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Welcome to ACCMS-8

We are pleased to announce that the 8th Conference of Asian Consortium on


Computational Materials Science (ACCMS-8) will be held at the National Taiwan
University of Science and Technology (NTUST), Taipei, Taiwan on June 16-18, 2015.
ACCMS was established in 2000 to nurture and promote research and development
activities in computational materials in Asian countries. The first Asian Consortium
on Computational Materials Science (ACCMS-1) was successfully held in Bangalore,
India in 2001. Then, the meeting was held in Russia (Novosibirsk, ACCMS-2 2004),
China (Beijing, ACCMS-3 2005), Korea (Seoul, ACCMS-4 2007), Vietnam (Hanoi,
ACCMS-5 2009), Singapore (ACCMS-6 2011), and Thailand (Nakhon Ratchasima,
ACCMS-7 2013). In the last ACCMS-7, more than 240 participants from 24 countries
enjoyed academic discussions and nature circumstances in Thailand.
ACCMS-8 will continue the tradition of ACCMS. In ACCMS-8, computational
physicists, chemists and material scientists will gather to discuss important issues and
to share essential progresses in various fields such as biotechnology, catalysis,
spintronics, electron transport, thermoelectric effect, energy applications, and etc.
We hope that you will take the opportunity to network with new acquaintances, and to
build upon those relationships that have already been established. We look forward to
welcoming our friends and colleagues from Asia, as well as other parts of the world.

Sincerely yours,
Professor Jyh-Chiang Jiang, NTUST
Dr. Jer-Lai Kuo, IAMS, Academia Sinica

Organizers
The main committees are from nearby institutes: National Taiwan University of
Science and Technology (NTUST), National Taiwan University (NTU), National
Taiwan Normal University (NTNU), and Institutes of Atomic and Molecular Sciences,
Academia Sinica (IAMS, AS). Participants are also welcome to visit our campuses
and also academic groups within.
Local Organizing Committee

Jyh-Chiang Jiang (Department of Chemical Engineering, NTUST) [Chair]

Jer-Lai Kuo (IAMS, Academia Sinica, Taiwan) [Chair]

Chao-Ping Hsu (Institute of Chemistry, Academia Sinica, Taiwan)

Chih-Kai Yang (Graduate Institute of Applied Physics, National Chengchi


University)

Yu-Chang Chen (Department of Electrophysics, National Chiao Tung


University)

Kaito Takahashi (IAMS, Academia Sinica, Taiwan)

Ming-Kang Tsai (Department of Chemistry, NTNU)

Yun-Wen Chen (IAMS, Academia Sinica, Taiwan) [Secretary]

International Program Committee:

Vladimir Belosludov (Nicolaev Institute of Inorganic Chemistry, Russia)

Khian-Hooi Chew (University of Malaya, Malaysia)

Gour Prasad Das (Indian Association for the Cultivation of Science, India)

Yuan Ping Feng (National University of Singapore, Singapore)

Xin-Gao Gong (Fudan University, China)

Jisoon Ihm (Seoul National University, Korea)

Puru Jena (Virginia Commonwealth University, USA)

Yoshiyuki Kawazoe (Tohoku University, Japan)

Vijay Kumar (VKF and Shiv Nadar University, India)

Kwang-Ryeol Lee (Korea Institute of Science and Technology, Korea)

Sukit Limpijumnong (Suranaree University of Technology, Thailand)

Duc Nguyen (Culham Centre for Fusion Energy, UK)

John S. Tse (University of Saskatchewan, Canada)

Enge Wang (Peking University, China)

Schedule

2015 6/16 Tuesday


08:00~08:45

REGISTRATION

08:45~09:00

OPENING: Mei-Yin Chou, IAMS DIRECTOR

09:00~09:45

PLENARY 1: John S. Tse

09:45~10:00

10:00~12:00

COFFEE BREAK
Section 1A

Section 1B

Section 1C

Rauzah Hashim,

Vladimir Belosludov,

Makusu Tsutsui,

Vannajan Sanghiran Lee,

Toshiaki Iitaka,

Yu-Hui Tang,

Ming-Hsien Lee,

Chin-Lung Kuo,

Chao-Cheng Kaun,

Lam K. Huynh

Ying Chen

Ilias Amanatidis

12:00~13:30

13:30~15:00

LUNCH
Section 2A

Section 2B

Section 2C

Hui-Hsu Gavin Tsai,

Guang-Yu Guo,

Xin-Gao Gong,

Jiann T'suen Lin,

Jisoon Ihm,

Yu-Chang Chen,

Yu-Tai Tao

Balazs Hetnyi

Patrick Sit

15:00~15:30

15:30~16:30

COFFEE BREAK
Section 3A

Section 3B

Section 3C

Hockseng Nguan,

Hirobumi Mineo,

Tzu-Jen Lin,

Yun-Wen Chen,

Yu-Lin Yeh,

Yulia Yu. Bozhko,

Arkapol Saengdeejing

Ermias Girma Leggesse

Santhanamoorthi Nachimuthu

16:30~17:00

17:00~18:30

Chair: Mei-Yin Chou

COFFEE BREAK
Section PA

Section PB

POSTER FLASH

POSTER FLASH

TALKS

TALKS

18:30~19:00

Dinner/Poster Prepare

19:00~20:00

POSTER SESSION

2015 6/17 Wednesday


08:30~09:00
09:00~09:45

REGISTRATION
PLENARY 2: Peijun Hu

09:45~10:00

10:00~12:00

COFFEE BREAK
Section 4A

Section 4B

Section 4C

Shang-Bin Liu,

Qiang Sun,

Duc Nguyen-Manhm

Aloysius Soon,

Hongming Weng,

Kwang-Ryeol Lee,

Shawn D. Lin,

Viet Huy Nguyen,

Hiroshi Mizuseki,

Hsin-Tsung Chen

Hung-Chung Hsueh

Koji Akai

12:00~13:30

13:30~15:00

LUNCH
Section 5A

Section 5B

Section 5C

Satoshi Watanabe,

Qian Wang,

Vijay Kumar,

Jian-Tao Wang,

Su Ying Quek,

Gang Lu,

Chee Kwan Gan,

Chih-Kai Yang

Kahyun Hur

15:00~15:30

15:30~17:40

Chair: Jyh-Chiang Jiang

COFFEE BREAK
Section 6A

Section 6B

Section 6C

Toyoko Imae,

Swapan K. Ghosh,

Manoj Harbola,

Gour Prasad Das,

Seungwu Han,

Jeng-Da Chai,

Wei-Hung Chiang,

Jiraroj T-Thienprasert,

Ryoji Sahara,

Shi-Hsin Lin,

Katsumi Hagita,

Miao Miao Wu

Sirichok Jungthawan

Chih-Kai Lin

Cheng-chau Chiu

17:40~18:30

Goto Banquet
BANQUET

2015 6/18 Thursday


08:30~09:00
09:00~09:45

REGISTRATION
PLENARY 3: Puru Jena

09:45~10:00

10:00~11:30

11:40~12:30

Chair: Jer-Lai Kuo

COFFEE BREAK
Section 7A

Section 7B

Section 7C

Yuan Chung Cheng,

Khian-Hooi Chew,

Hieu Chi Dam,

Elise Yu-Tzu Li,

Zhifeng Liu,

Yansun Yao,

Kaito Takahashi

Yasuhiro Senda

Jyh-Shing Lin

SPECIAL TALK by Yoshiyuki Kawazoe + CLOSING/AWARD


LUNCH

Oral Presentation
2015 6/16 Tuesday
PLENARY 1, IB 101

John S. Tse
09:00~09:45

Page 20

Order out of Disorder:


Pressure-induced Devitrification of Glasses

Section 1A, IB 101

(Chair: Khian-Hooi Chew)

Rauzah Hashim

10:00~10:30

Page 24

Structural and Dynamical Properties of Anhydrous Bilayers from Sugar Based Lipids:
An Atomistic Simulation Study
Vannajan Sanghiran Lee

10:30~11:00

Page 25

Theoretical antiviral protein design targeting HIV-1 capsid through molecular


dynamics simulations
Ming-Hsien Lee

11:00~11:30

Page 26

Lone Pair Electrons and Second Harmonic Generation in Oxide Crystals: A DFT
Study
Lam K. Huynh

11:30~12:00

Page 27

A Computational Study on the Adsorption Configurations and Reactions of


SiHX(X=1-4) on Clean and H-covered Si(100) Surfaces

Section 1B, IB 201

(Chair: Jisoon Ihm)

Vladimir Belosludov

10:00~10:30

Theoretical Study of the Boson Peak Origin in the Low Density Amorphous Ice
Toshiaki Iitaka

10:30~11:00

Page 30

Atomic-Scale Modeling of the Mechanical and Dielectric Properties of the


Ultra-Low-k Nanoporous Silicate Glasses
Ying Chen

11:30~12:00

Page 29

X-ray Raman Spectroscopy Measurement for Detecting Pressure-induced


Dissociation of Water Molecules in Ice VII
Chin-Lung Kuo

11:00~11:30

Page 28

Page 31

Elastic Properties of Dilute Si in Fe-Si Alloy and Effect of Ni-Doping: An Integrated


Study Based on First-Principles

Section 1C, IB 202


10:00~10:30
10:30~11:00
11:00~11:30
11:30~12:00

(Chair:Yu-Chang Chen)

Makusu Tsutsui

Page 32

Single-Molecule Sequencing Using Nanopores and Nanoelectrodes


Yu-Hui Tang

Page 33

Spin Torque Effect in Spin-Filter Based Magnetic Tunnel Junction


Chao-Cheng Kaun

Page 34

Spin-polarized Transport through Single-molecule Magnetic Junctions


Ilias Amanatidis

Page 35

Local Heating and Cooling criterion in Nanoscale Systems

Section 2A, IB 101

(Chair: Chao-Ping Hsu)

Hui-Hsu Gavin Tsai

13:30~14:00

Page 36

Computational Investigation of Electron Injection of Squaraine Dye-Sensitized Solar


Cells
Jiann T'suen Lin

14:00~14:30

Page 37

Metal-Free Sensitizers for Dye-Sensitized Solar Cells: Structure/Performance


Correlation
Yu-Tai Tao

14:30~15:00

Page 38

Polyfused Aromatics as Charge Transport Materials in Field-Effect Transistor


Applications: A Structure-Property Correlation Study

Section 2B, IB 201

(Chair: Gour Prasad Das)

Guang-Yu Guo
13:30~14:00

14:00~14:30

14:30~15:00

Ab Initio Calculation of Plasmon Excitations in Graphene and Nonlinear Optical


Properties of Transition Metal Dichalcogenide Monolayers
Jisoon Ihm

14:00~14:30

Page 40

Magnetic ordering on edges of topological insulators


Balazs Hetnyi

Page 41

The Topology of Ideal Conduction

Section 2C, IB 202


13:30~14:00

Page 39

(Chair:Duc Nguyen-Manhm)

Xin-Gao Gong

Page 42

Inverse Design and Computational Studies of Novel Solar Energy Materials


Yu-Chang Chen

Page 43

Thermoelectric properties in atomic/molecular junctions from first principles

14:30~15:00

Patrick Sit

Page 44

First Principles Study of Redox Reactions for Energy Storage and Conversion

Section 3A, IB 101

(Chair: Chao-Ping Hsu)

Hockseng Nguan

15:30~15:50

Page 45

Dynamics and Anomalous diffusions in the liquid crystals inverse hexagonal phase: a
molecular dynamics simulation study
Yun-Wen Chen

15:50~16:10

Page 46

Theoretical Investigation of Using Silsesquioxane Frameworks for Hydrogen Storage


System
Arkapol Saengdeejing

16:10~16:30

Page 47

First-principles study of stability of Cu in the Nd-rich and Nd Oxide phases of


Nd-Fe-B permanent magnet

Section 3B, IB 201

(Chair: Ming-Kang Tsai)

Hirobumi Mineo

15:30~15:50

15:50~16:10

Page 48

Adiabatic treatment for vibrational predissociation of water dimers with channel


interactions
Yu-Lin Yeh

Page 49

A Theoretical Investigation of Surface-enhanced Sum-Frequency Generation


Ermias Girma Leggesse

16:10~16:30

New Conductive Imidazole-derived Salt for Lithium-ion Battery Electrolytes: a DFT


study

Section 3C, IB 202


15:30~15:50

Page 50

(Chair: Kaito Takahashi)

Tzu-Jen Lin

Page 51

Predicting New Phases of Solid Methanol


Yulia Yu. Bozhko

15:50~16:10

Page 52

Modeling of Composition and Formation Conditions of Double Hydrates of


Tetrafluoromethane or Nitrous Oxide with methane
Santhanamoorthi Nachimuthu

16:10~16:30

Enhanced Hydrogen Storage Performance of Boron-doped Graphene decorated by


Ni-Ti-Mg atoms -A DFT study

Flash Talks
17:00~18:30
18:30~20:00

Page 53

(Chairs: Ming-Kang Tsai, Kaito Takahashi)

Section PA at IB 201;

Section PB at IB 202

POSTER SESSION and RECEPTION

12F

2015 6/17 Wednesday


PLENARY 2, IB 101

Peijun Hu
09:00~09:45

Page 21

Rational Catalyst Design in Heterogeneous Catalysis:


Density Functional Theory Studies

Section 4A, IB 101

(Chair: Jyh-Chiang Jiang)

Shang-Bin Liu

10:00~10:30

Page 54
31

A Novel Acidity Scale for Acidic Catalysts Based on P NMR Chemical Shifts of
Phosphine Oxide Probe Molecules
Aloysius Soon

10:30~11:00

Page 55

Non-conventional supports for single-atom nanocatalysts for the oxygen reduction


reaction
Shawn D. Lin

11:00~11:30

Page 56

Metal-oxide interface for sustainable hydrogen production with ethanol steam


reforming over Cu-NiO catalyst
Hsin-Tsung Chen

11:30~12:00

Page 57

CO Oxidation and C2H4 Epoxidation Catalyzed by a Gold Nanoparticle: : A


Computational Study

Section 4B, IB 201

(Chair: Chih-Kai Yang)

Qiang Sun

10:00~10:30

Page 58

Phase Stability of Dichalcogenide Monolayers


Hongming Weng

10:30~11:00

Page 59

Quantum Spin Hall Effect in 2D Transition Metal Dichalcogenide Haeckelites


Viet Huy Nguyen

11:00~11:30

11:30~12:00

Page 60

Improving Performance of Electronic and Thermoelectric Graphene Devices by


Strain Engineering
Hung-Chung Hsueh

Page 61

Dimensionality Effects on Bound Excitons in Few-layer BN

Section 4C, IB 202

(Chair: John S. Tse)

Duc Nguyen-Manhm

10:00~10:30

Page 62

Nano-defect clusters in irradiated materials: First-principles assessment and


multi-scale modelling

Kwang-Ryeol Lee

10:30~11:00

Page 63

Multiscale Simulation Study of Structure and Electronic Properties of Oxidized


Silicon Nanowire
Hiroshi Mizuseki

11:00~11:30

Page 64

Materials Design on Energy-related Materials by Multiscale Simulations


Koji Akai

11:30~12:00

Page 65

Study of electronic structures and thermoelectric properties on conjugated


ethylenetetrathiolate metal polymers

Section 5A, IB 101

(Chair: Xin-Gao Gong)

Satoshi Watanabe

13:30~14:00

Page 66

First-Principles Study on Electric and Dielectric Properties of Metal-Oxide


Heterostructures in Nanoscale Devices
Jian-Tao Wang

14:00~14:30

Page 67

Three-connected Networks of Si in Disilicides


Chee Kwan Gan

14:30~15:00

Page 68

Phononic Properties of Metal Chalcogenides Bi2S3 and Sb2S3: A First-Principles


Study

Section 5B, IB 201

(Chair: Puru Jena)

Qian Wang

13:30~14:00

Page 69

A Pentagon Based Carbon Sheet


Su Ying Quek

14:00~14:30

Page 70

Quantum-confinement and Structural Anisotropy result in Electrically-Tunable Dirac


Cone in Few-layer Black Phosphorous Importance of interlayer interactions
beyond van der Waals
Chih-Kai Yang

14:30~15:00

Page 71

Graphene, Graphane, and Their Composites

Section 5C, IB 202

(Chair: Kwang-Ryeol Lee)

Vijay Kumar

13:30~14:00

CsSn(XxY1-x)3 (X and Y = Cl, Br, and I) mixed perovskites for photovoltaics


Gang Lu

14:00~14:30

Page 73

Exciton Diffusion and Charge Separation in Organic Photovoltaics


Kahyun Hur

14:30~15:00

Page 72

Page 74

Linking Experiment and Theory for 3D Networked Binary Metal Nanoparticle


-Triblock Terpolymer Superstructures

10

Section 6A, IB 101

(Chair: Jyh-Chiang Jiang)

Toyoko Imae

15:30~16:00

Page 75

Roles of Amine and Iron Oxide on Exfoliation of Graphite


Gour Prasad Das

16:00~16:30

Page 76

Electronic structure and Transport properties of Graphene Nanoribbons


Wei-Hung Chiang

16:30~17:00

Page 77

Atmospheric-pressure controllable synthesis of heteroatom-doped carbon


nanomaterials and its applications for electrochemical energy storage and conversion
Shi-Hsin Lin

Page 78

17:00~17:20
Activation and Tuning of Two-dimensional Materials for Hydrogen Evolution Reaction
Sirichok Jungthawan

17:20~17:40

Page 79

Deformation behavior of strained single-layer BN, graphene, and silicene under


pressurized blister test

Section 6B, IB 201

(Chair: Vijay Kumar)

Swapan K. Ghosh

15:30~16:00

Page 80

Energy Density Functional Approach to Designing Functional Materials for Energy


Applications
Seungwu Han

16:00~16:30

Page 81

Automatizing Ab initio Calculations for High-throughput Screening


Jiraroj T-Thienprasert

16:30~17:00

Page 82

First-principles study of M defects (M = Bi and Al) in orthorhombic PbZrO3


Katsumi Hagita

17:00~17:20

Page 83

Study of phonon DOS of Carbon crystals from nested K4 lattice to BC-8 structure
Chih-Kai Lin

17:20~17:40

Nitrogen Dopants and Vacancy Defects in Graphene Nanoflakes: Theoretical Study


of Size-Dependent Electronic Excitation Properties

Section 6C, IB 202


15:30~16:00
16:00~16:30

Page 84

(Vladimir Belosludov)

Manoj Harbola

Page 85

Excited-state energy functionals and ionization potential theorem


Jeng-Da Chai

Page 86

TAO-DFT and Its Applications to Zigzag Graphene Nanoribbons

11

Ryoji Sahara

16:30~17:00

Page 87

First principles study of electronic structures and stability


in structural materials
Miao Miao Wu

17:00~17:20

Page 88

Photoelectron Spectroscopy and Theoretical Study of Platinum Halides PtXn (X = F,


Cl, Br, I; n = 2-4)
Cheng-chau Chiu

17:20~17:40

Page 89

Ru Catalyzed Hydrodeoxygenation of Aromatic Oxygenates Derived from Biomass

2015 6/18 Thursday


PLENARY 3, IB 101

Puru Jena
09:00~09:45

Superhalogens A Bridge between Complex Metal Hydrides and


Li-ion Batteries

Section 7A, IB 101

(Chair: Yoshiyuki Kawazoe)

Yuan Chung Cheng

10:00~10:30

Page 90

Theory for Electronic Couplings and Dynamics of Singlet Fission in Oligoacene


Dimers
Elise Yu-Tzu Li

10:30~11:00

11:00~11:30

Page 91

Factors Governing Strong Spin-Orbit Coupling and Fast Intersystem Crossing in


Luminescent Materials: A Theoretical Perspective
Kaito Takahashi

Page 92

Tug of war between H3O+ versus Ar/OH

Section 7B, IB 201


10:00~10:30

(Chair: Qian Wang)

Khian-Hooi Chew

11:00~11:30

Page 93

Charge Compensation Phenomena at Ferroelectric Interface


Zhifeng Liu

10:30~11:00

Page 22

Page 94

Designing Nano-Valves for the Storage of Hydrogen under High Pressure


Yasuhiro Senda

Page 95

Atomic force microscopy simulation covering wide range time-scale

12

Section 7C, IB 202


10:00~10:30

(Chair: Qiang Sun)

Hieu Chi Dam

Page 96

Sparse Modeling for Materials Design


Yansun Yao

10:30~11:00

Page 97

Computational Material Discovery using the HPC-Based ab initio Methods


Jyh-Shing Lin

11:00~11:30

Page 98

Theoretical study of reaction dynamics for C-X dissociation of


XH2C-CCH(ads)/X-CCCH3(ads) (X= I and Br) adsorbed on Ag(111) surface

Special Session, IB 101


Yoshiyuki Kawazoe
11:40~12:10

Page 99

Theoretical Study on Task Specific Ionic Liquid for Metal Extraction from
Garbage Caused by Tsunami

13

Poster Presentation
Rujun Song

01

02
03

Numerically Study of the Aerodynamic Response and Energy Harvesting of Polyvinylidene


Fluoride Piezoelectric Harvester in a Uniform Flow
Surya Velappa Jayaraman

Surya Velappa Jayaraman

08

10

Jeongwoon Hwang

13
14

Page 108

Sp2-dominant amorphous carbon film for durable silicon anodes for lithium-ion batteries
Page 109

The Effect of Different Substitution on Bis(trifluoroborane)-benzimidazole Lithium Salts for


Battery Electrolytes
Chuan-Hui Zhang

Page 110

The Influence of Chloride Ions Preference Adsorption on -Al2O3 (0001) Surface

Page 111

Theoretical Insights into the Effect of Water on the Oxidative Decomposition of Propylene
Carbonate in Lithium Ion Batteries
Ting Yi Wei

12

Page 107

Lithiation Mechanism and Origin of Enhanced Lithium Storage Capacity for Functionalized
Graphene Nanoribbons : A First-Principles Study

Ting Yin Chen

11

Page 106

Insights into Li-ion Diffusion Mechanisms in Novel Fluorophosphates Li9Mg3[PO4]4F3 Cathode


Material for Lithium-ion Batteries: A First Principles Study

Tun Sriana

09

Page 105

Ab initio random structure searching: Applications to Li adsorption, hydrogen storage, and


dissociation on monolayer MoS2

Kun Han Lin

07

Page 104

The thermoelectrochemical effect in Protic Ionic Liquids: A Molecular Thermodynamic


Approach

Meng-Han Li

06

Page 103

Investigation on Pair Stability of Imidazolium Cations with PGM Chloroanions

Darwin Barayang Putungan

05

Page 102

A DFT Study on Properites of [BMIM][NTF2] IL Functionalized with Alkyl Amine Chains

Syafie Mahmood

04

Page 101

Page 112

High-Throughput Virtual Screening of Sulfone-Based Electrolytes for High-Voltage Li-Ion


Batteries
Han-Hsin Chiang

Page 113

Ab-initio Study for Dopant Effects on the Lithiation Processes of c- Si


Fa-Chieh Chu

Page 114

Spin Torque Effect in BeO-based Magnetic Tunnel Junction

14

Cheng Wei David Gu

15

Quantum transport properties of Au/oligothiophene/Au single molecular junctions: A


first-principles study
Kan Yeep Choo

16

19

Woosun Jang

23

25

Liang-Chun Lin

Page 124

Theoretical Study of the Acousto-Optic Low Frequency Resonance-like Vibration Behaviour in


the High Density Amorphous Ice
Taku Mizukami

Page 125

Hydration Water Behavior Characterization by Simulation-Based Data-Mining Approach


Page 126

Molecular Dynamics Simulations of Polyethylene Glycol Monolaurate in Water and in Aliphatic


Alcohols
Page 127

Hydration and Thermal effects on Structure and Dynamic Properties of Mono- and Guerbet
Branched-chain -D-Maltosides: An Atomistic Simulation Study
I-Shou Huang

28

Page 123

Negative temperature dependance of atmospherically significant R1R2COO+ Water reaction

Vijayan Manickam Achari

27

Page 122

An Ontological Account on the Spectral Signatures of an Ionic Hydrogen Bond in Some Zundel
Type Structures

Ianatul Khoiroh

26

Page 121

Anharmonicity Calculation of O-H Stretching Motion in Small Methanol Clusters along Normal
Coordinates

Kirill V. Gets

24

Page 120

Structural and Bonding Properties of AuSin- (n=4-12) and AuGen- (n=2-12) Clusters:
Photoelectron Spectroscopy and Density-Functional Calculations

Jake Acedera Tan

22

Page 119

A density-functional theory study of the opto-electronic properties of polymorphic WO3

Hsiao-Han Chuang

21

Page 118

Theoretical Calculations on Photochemistry of Irgacure 907


(2-Methyl-4-(methylthio)-2-morpholinopropiophenone) and Newly Designed Photoinitiator

Hong-Guang Xu

20

Page 117

Effects of different adsorption modes of sensitizers on TiO2 on the dye loading, absorption
spectra and electron injection properties in dye-sensitized solar cells: A DFT/TD-DFT study
Wan-Rou Tong

18

Page 116

Dispersive Charge Trasport Study in Periodic Structures of Crytalline- Amorphous Hybrid


Organic Materials
Jia Cheng Hu

17

Page 115

Page 128

Laying the Foundations of a Non-Linear Adaptive Force Matching Algorithm: An Economic,


Systematic, & ab initio Derived Re-Parameterization of a Simple Water Model

15

Wei Lim Chong

29

Page 129

High Speed Molecular Dynamics Simulations in Designing Ankyrin that Interact with E protein
of Dengue Virus II
Vertika Gautam

30

Page 130

GPU accelerated Molecular Dynamics Simulations in the Designing of Ankyrin as specific


binders of ERK2
Chia Jen Hsu

31

Page 131

Searching for GSK3b Kinase Inhibitros: Molecular Docking, Molecular dynamics Simulation,
and Kinase Assay
Yin Cheng Chen

32

33

Page 132

Characterization of Shape Resonances on Trimethyl Phosphite, Trimethyl Phosphate, and


Phosphoryl Chloride
Narasak Pandech

Page 133

First Principles Calculations of Elastic Parameters of Perovskite Oxides


Gou-Tao Huang

34

Page 134
III

-L] System (L =

H/Me)
Chen-Hao Yeh

35

36

Density Functional Theory Calculation on the Dissociation Mechanism of Nitric Oxide


Catalyzed by Cu4 cluster in ZSM-5 (Cu4-ZSM-5) and Bimetal Cu3Fe in ZSM-5 (Cu3Fe-ZSM-5)
Thanundon Konknok

38
39

41
42

Duc-Long Nguyen

Page 138

Alkaline earth metal halides: New candidate 2D materials


Yuwadee Suwan

Page 139

Theoretical Study of Gas Diffusion Through Porous Graphene Under Pressure


Page 140

Particle size effects of sulfonated graphene supported Pt nanoparticles on ethanol


electrooxidation: combined experiment and DFT study
Icuk Setiyawati

Page 141

Magnetic Property of Fullerene C20 : A First-Principles Study


Katsumi Hagita

Page 142

Stability study of ring-like sheet of Ag atoms wrapping CNT


W. C. Chen

43

Page 137

First Principles Study of the Doping Effect on Graphene from the Sn impurities in the SiO2
Substrates

Yi En Liu

40

Page 136

First-Principles Study of Alkali Metal Intercalated in Transition Metal Dichalcogenides


An Ho

37

Page 135

Page 143

Density Function Theory Used to Investigate the Adsorption and Charge Transfer in the
Tri-iodine-Pt(111) Slab Surfaces Interaction

16

44

Kai-Hao Tsau

Ethylene Carbonate Adsorption and Decomposition on LixMn2O4 Cathode: A DFT study


P. L. Lu

45

51

53

Chia Ni Li

56
57
58

Page 152

Computational study of hydrogen storage in quasi-2 dimensional potential well of K-intercalated


graphite oxide layered structure
Amol Deshmukh

Page 153

Tetrahedral Silsesquioxane Framework: A Feasible Candidate for Hydrogen Storage


Page 154

Influence of non-local van der Waals corrections on the bulk and surface properties of pristine
metals
Batjargal Sainbileg

55

Page 151

Ammonia synthesis by Nitrogen and Hydrogen on W(111)surface:A Computational Study

Ji-Hwan Lee

54

Page 150

Density-functional Calculations of Methane Conversion on Platinum Decorated Graphene


Oxide Sheets

Jaehyun Bae

52

Page 148

Combined Experiment and DFT Investigations of FePt Nanodentrites with High-index Facets
as Active Electrocatalysts for Oxygen Reduction Reaction
Shiuan-Yau Wu

50

Page 148

Methane and Ethane Oxidative Dehydrogenation Mechanism on MoO3 and Transition Metal
Doped MoO3 Surfaces
Hung Lung Chou

49

Page 147

Catalytic Enhancement of the Dehydrogenation of Propane to Propylene on Rhodium


Nanoclusters (Rh13) Supported on Unzipped Graphene Oxide A DFT Study
Chen Cheng Liao

48

Page 146

Formaldehyde Decomposition on Boron Doped Graphene Decorated with Transition Metal


Atoms A First Principles Study
Chun-Chih Chang

47

Page 145

Density Function Theory Used to Investigate the Adsorption and Dissociation of O2 on


FexPt1-x(111) and Pt(111) and Fe(100) Slab Surfaces
Yi-Pin Lin

46

Page 144

Page 155

Raman spectra - crystal packing structures relationship in P3HT: A first-principles DFT


investigation
Alexandra Santos-Putungan

Page 156

Structural and Magnetic Properties of Zn0.5Co0.5O Alloy Configurations via DFT


Muhammad Anshar Makhraja

Page 157

Ab initio-aided thermodynamic reassessment of the Mo-Zr binary system


Swastibrata Bhattacharyya

Page 158

The First-principles Mapping onto the Phase Field Crystal Model

17

59
60
61
62
63

Kittiphong Amnuyswat

Page 159

Hybrid Functional Calculation of Defects in Pseudo-Binary Indium Oxynitride


Yonghyuk Lee

Page 160

A first-principles study of the mechano-thermodynamics of super-ultrahard materials


Jong Hyun Jung

Page 161

Numerical Calculation on Controlled Oscillatory Cracks in Glass Film on Substrate


Chou-Hsun Yang

Page 162

First-Principle Characterization for Electronic Coupling in Singlet Fission


Bo-Chao Lin

Page 163

Theoretical Investigation of Charge Transfer Processes at Pentacene-C60 Interface

18

PLENARY PRESENTATIONS

19

Order out of Disorder: Pressure-induced Devitrification


of Glasses
Wu Min1, H. Liu2 and John S. Tse1,2
1
Department of Physics and Engineering Physics,University of Saskatchewn,
Saskatoon, Saskatchewan, Canada S7N 5B2
2
State Labooratory of Superhard Materials, Jilin University,Changchun, China
0. Phase transitions in amorphous alloys under pressure are an important
fundamental problem. Here we report on first-principles study on the classic
case of SnI4 and a Ce75Al25 metallic glass that have been reported to become
crystalline solids under compression.
Contrary to common belief,
pressure-induced devitrification of the amorphous CeAl alloy is not due to
the Ce 4f delocalization that is expected to bring the size of Ce atoms closer to
that of Al atoms and the analysis show the HumeRothery rules are not
applicable at high pressure. In fact, a continuous increase in the relative
Ce/Al Bader volume leads to favourable conditions for forming a
close-packed structure at high pressure by the dominant Ce [1]. A similar
observation is found in SnI4 [2]. In this case, the size, of the Sn atoms are
substantially reduced due to charge transfer to the I and the crystal packing is
dominated by the Sn atoms. . This study provides a new perspective on the
electron (re)distribution in solids under pressure. The theoertical results will
also be compared to the prediction from recent theorical models on closet
packed diirorder binary solids.
[1] M.Wu, J.S. Tse, S.Y. Wang,
C.Z. Wang and J.Z. Jiang, Nature Comm., 6,
doi:10.1038/ncomms7493 (2015).
[2] H. Liu, J.S. Tse, M.Y. Hu, W. Bi, J Zhao, E.E. Alp, M. Pasternak,R.D.
Taylor and J.C. Lashley, to be submitted (2015)

Contact: J.S. Tse, John.Tse@usask.ca

20

Rational Catalyst Design in Heterogeneous Catalysis:


Density Functional Theory Studies
Peijun Hu
Queens University Belfast
Rational catalyst design in heterogeneous catalysis is one of the ultimate goals in
physical science. In this talk, firstly I will present some of our work on the
understanding of activity of heterogeneous catalysts. The activity of catalysts, the
so-called volcano curve, will be discussed and some key properties for the activity of
catalysts will be identified. Finally, I will show how the understanding of activity of
catalysts from DFT studies can be used to rationally design new catalysts in
heterogeneous catalysis.

21

Superhalogens A Bridge between Complex Metal Hydrides


and Li-ion Batteries
Puru Jena
Physics Department, Virginia Commonwealth University, Richmond, VA 23284-2000
Abstract
Complex metal hydrides and Li-ion batteries play an integral role in the
pursuit of clean and sustainable energy. The former stores hydrogen and can provide a
clean energy solution for the transportation industry while the latter can store energy
harnessed from the sun and the wind. However, considerable materials challenges
remain in both cases and research for finding solutions has traditionally followed
parallel paths. I will show that there is a common link between these two seemingly
disparate fields which can be unveiled by studying the electronic structure of the
anions in complex metal hydrides and in electrolytes of Li-ion batteries; they are both
superhalogens [1]. I will also demonstrate that considerable progress made in our
understanding of superhalogens in the past decade can provide solutions to some of
the material challenges in both these areas.
1. P. Jena, Superhalogens-A Bridge Between Complex Hydrides and Li-ion
Batteries, J. Phys. Chem. Letters 6, 1119 (2015) (invited perspective)

22

ORAL PRESENTATIONS

23

Structural and Dynamical Properties of Anhydrous Bilayers


from Sugar Based Lipids: An Atomistic Simulation Study
Rauzah Hashim1 , Vijayan ManickamAchari1, Richard A. Bryce2
1

Center for Fundamental and Frontier Science in Nanostructure Self-Assembly


Chemistry Department, University of Malaya, Kuala Lumpurm Malaysia
2
Manchester Pharmacy School , University of Manchester, Manchester, United
Kingdom

Glycolipids form materials of considerable potential for a wide range of


surfactant and thin film applications. Understanding the effect of glycolipid covalent
structure on the properties of their thermotropic and lyotropic assemblies is a key step
towards rational design of new glycolipid-based materials. We have studied the dry
properties (both static and dynamics) of the synthetic glycolipids, dodecyl
-maltoside, dodecyl -cellobioside, dodecyl -isomaltoside and a C12C10 branched
-maltoside using molecular simulations. Amongst the properties we have examined
include alkyl chain conformations, relaxation times of the hydrophilic and
hydrophobic regions of the glycolipids, and lipid diffusion. We find monoalkylated
glycolipids possess a small amount of gauche conformers (~15%) in the lamellar
crystal (LC) phase, implying the hydrophobic region is in a disordered liquid phase. In
contrast, the branched chain glycolipid system in the fluid L phase shows higher
gauche population (2030%) similar to hydrated phospholipid systems in the same
phase. The presence of gauche conformations in cell membranes at low temperature
provides a resistance mechanism to facilitate and regulate the cell activity at a
minimum rate to prevent the cell from becoming dormant. Compared to the alkyl
chain, the headgroup relaxation time is shorter and varies with different sugar groups:
that of the isomaltoside is the longest, which is in a qualitative agreement with a
dynamic study for a gentiobioside (similar to isomaltoside) using 2H-NMR. The nonreducing sugar, relaxes faster relative to the reducing sugar. In the LC phase, lateral
diffusion of glycolipids is in the ascending order of maltoside, isomaltoside and
cellobioside. These values of lateral diffusion are found to be ~10 fold slower than
that of the branched chain lipid in the L phase. Moreover, compared to hydrated L
phospholipids, the lateral diffusion for the anhydrous branched chain glycolipid is
about 36 times slower. Developing an understanding of the relationship between
glycolipid structure and dynamics is important in guiding the rational design of
glycolipids with tailored properties, for example in formulation.
Contact: rauzah@um.edu.my

24

Theoretical antiviral protein design targeting HIV-1 capsid


through molecular dynamics simulations
Vannajan Sanghiran Lee,1, 2 Hana Atiqah Abdul Karim,1, 2 Sharifuddin Md. Zain,1
Noorsaadah Abd Rahman,1 Piyarat Nimmanpipug,3 and Chatchai Tayapiwatana4
1

Drug Design and Development Research Group, Department of Chemistry, University


of Malaya, Kuala Lumpur, Malaysia
2
Center for Theoretical Physics, University of Malaya, Kuala Lumpur, Malaysia
3
Computational Simulation Modelling Laboratory (CSML), Department of Chemistry and
Center of Excellence for Innovation in Chemistry and Materials Science Research Center,
Faculty of Science, Chiang Mai University, Chiang Mai, Thailand
4
Biomedical Technology Research Unit, National Center for Genetic Engineering and
Biotechnology, National Science and Technology Development Agency at the Faculty of
Associated Medical Sciences, Chiang Mai University, Thailand

Computer simulations are used to rationalize and guide experiments for novel protein
with improved binding affinity at an atomic level. Molecular docking, molecular
dynamics simulation (MD) coupled with molecular mechanics generalized Born
surface area (MM-GBSA)/molecular mechanics PoissonBoltzmann surface area
(MM-PBSA) and computational alanine scanning have been applied to analyze the
binding interaction. A speedaccuracy trade-off protocol for protein mutation and
docking in designing the protein with improved binding activity toward the protein
target has been developed.
Our novel designed protein inhibitors system e.g. antibody [1, 2] and ankyrin
targeting HIV-1 capsid [3] will be discussed. As a result, the importance of the
residues which highly affect by alanine scanning of scFv anti-p17 and the key
interaction residues from pairwise decomposition energy calculation were identified.
MET100, LYS101, ASN169, HIS228, and LEU229, play a crucial role in the binding
affinities with the HIV-1 p17 variants. With the guide from both methods, the novel
scFv M100G has been designed and confirmed by peptide ELISA results of their
activities with more viral strain. The electrostatic contributions have been a major part
in the antibody design while other parameters such as vdW, PB , and GB did
not show much variation. Another approach for inhibiting HIV infection using the
Designed Ankyrin Repeat Protein (DARPin) technology by interrupting the protein
assembly process has been investigated. Similarly, free energy of binding and its
decomposition per residue will be clarified to identify crucial residues involved in
improvement of target protein binding of the designed ankyrin.
[1] P. Tue-nguen, K. Kodchakorn, P. Nimmanpipug, N. Lawan, S. Nangola, C
Tayapiwatana, N.A. Rahman, S.M. Zain, and V. S. Lee, BioMed. Res. Int. 2013, 713585713597.
[2] V.S. Lee, P. Tue-ngeun, S. Nangola, K. Kitidee, J. Jitonnom, P. Nimmanpipug, S.
Jiranusornkul, and C. Tayapiwatana,. Mol. Imm. 2010, 47, 982-900.
[3] W. Praditwongwan, P. Chuankhayan, S. Saoin, T. Wisitponchai, V.S. Lee, S. Nangola,
S.S. Hong, P. Minard, P. Boulanger, C-J. Chen, and C. Tayapiwatana, J. Comput. Aided.
Mol. Des. 2014, 28:869884.

Contact: vannajan@gmail.com

25

Lone Pair Electrons and Second Harmonic Generation in


Oxide Crystals: A DFT Study
Ming-Hsien Lee,* Shyong K. Chen, Chun-Hong Lo and Tue-Hsiang Chueh
Department of Physics, Tamkang University,Tamsui, New Taipei City, Taiwan
2

Oxides have been the most important crystalline materials used for second harmonic
generation (SHG), where frequency conversion take place when input laser beam
induced a double frequency output photon in nonlinear optical (NLO) materials. In
this talk, we report a detailed first-principles mechanism study on the SHG effect in
oxides. Density functional theory based planewave pseudopotential method geared
for optical properties calculation is used in the present study, and sum over states
style formalism derived from length gauge perturbation theory is used to calculate the
SHG nonlinear optical property. We proposed a band-resolved scheme to analyse
contribution of SHG band-by-band, based on which what we defined as SHG density
can be visualised in real space, showing location in crystal where SHG effect are
strongest. With this method, the "hot spots" of electronic subsystem which contribute
most to SHG can be identified for further consideration of material design. The
results of oxide SHG density indicates lone pair electrons on oxygen atoms play very
important role. With a criterion we developed to visualise lone pair electron
distribution in crystal in real space, and by comparing SHG density and lone pair
density, we computationally proved that this is indeed the case.

Contact: mhslee@mail.tku.edu.tw

26

A Computational Study on the Adsorption Configurations and


Reactions of SiH X (X=1-4) on Clean and H-covered Si(100)
Surfaces
Thong N-M Le,1 P. Raghunath,2 L. K. Huynh,1,3* and M. C. Lin2*
1

Molecular Science and Nano-Materials Laboratory, Institute for Computational Science and
Technology, Quang Trung Software Park, Dist. 12, Ho Chi Minh City, Vietnam.
2
Center for Interdisciplinary Molecular Science, Department of Applied Chemistry, National Chiao
Tung University, Hsinchu 300, Taiwan.
3
International University, VNU-HCMC

All possible adsorption configurations of H and SiH X (x=1-4) on clean and H-covered Si(100)
surfaces are determined by using spin-polarized DFT calculations. The results show that, on the clean
surface, the gas-phase hydrogen atom and SiH 3 radicals effectively adsorb on the top sites, while SiH
and SiH 2 prefer the bridge sites of the first layer. Another possibility for SiH is to reside on the hollow
sites with a triple-bond configuration. For partially H-coverd Si(100) surface, the mechanism is
similar but with higher adsorption energies in most cases. This suggests that the surface species
become more stable in the presence of surface hydrogens. The minimum energy paths (MEPs) for the
adsorption/migration and reactions of H/SiH X species on the surfaces are explored using the climbing
image-nudged elastic band (CI-NEB) method. The competitive surface processes for Si thin-film
formation from SiH X precursors are also predicted. The study reveals that the migrations of hydrogen
adatoms are unimportant with respect to leaving open surface sites because of their excessively high
barriers. Alternatively, the abstractions of hydrogen adatoms by H/SiH X radicals are more
energetically favorable. Similarly, the removals of hydrogen atoms from adsorbed SiH X , essential
steps for forming Si layers, are dominated by the abstractions rather than decomposition processes.
The kinetic analysis, using our home-made SurfKin code [1], is also carried out for such processes at
real plasma-enhanced deposition temperatures, i.e., in a range of 300-600 K. Accordingly, the
following competitive channels are considered, namely, abstraction of surface hydrogens against
hydrogen migrations, and hydrogen abstractions from adsorbed species against hydrogen
decompositions. It is concluded that the abstraction channels play an important role in the formation
of sillicon thin films.

[1] Le, T. N., Liu, B. & Huynh, L. K., J. Comput. Chem. 35, 1890-1899, doi:10.1002/jcc.23704 (2014).

Contact: lamhuynh.us@gmail.com

27

Theoretical Study of the Boson Peak Origin in the Low


Density Amorphous Ice
Belosludov V.R.1,4, Gets K.V.1,4, Belosludov R.V.2,
Kawazoe Y.3,4 and Subbotin O.S.1,4
1

Nikolaev Institute of Inorganic Chemistry; SB RAS, Novosibirsk, Russia


2
Institute for Materials Research, Tohoku University, Sendai, Japan
3
New Industry Hatchery Center, Tohoku University, Sendai, Japan
4
Kutateladze Institute of Thermophysics, SB RAS, Novosibirsk, Russia

In this study we present the research of excess low-frequency vibrations,


which determine the Boson peak in low density amorphous ice (LDA).
The cubic model of LDA ice containing 512 rigid water molecules was
constructed and studied. Calculations were performed using a modified SPC/E
potential. The intermolecular interaction was described by the Coulomb interaction
(long-range interaction) and the van-der-Waals forces (short-range interaction). The
most energetically favorable structure of LDA ice was found using combination of
molecular dynamics method and conjugate gradient method. In this study the
approach [1], which considers the model cell as a unit cell of the pseudo-crystal. The
periodic boundary conditions also was applied to the model cell. Using this approach
and lattice dynamics method the dynamical characteristics and dispersion curves of
LDA ice structure were calculated along the pseudo Brillouin zone.
The results of simulation work reveal very good agreement of vibrational
density of states data with experimental data [2] of Boson peak research in LDA,
LDA ice and ice I h . We show that the main contribution to the excess low-frequency
vibrations is given by delocalized (crystal-like) collective translational vibrations. The
instantaneous displacement vectors of these vibrations of water molecules exhibit
crystalline optic vibration properties. The research of oxygen-oxygen radial
distribution function shows that the nature of boson peak in LDA ice is determined by
the hydrogen bond network.
The work was supported by Russian Megagrant (Project No. 14.B25.31.0030
New energy technologies and energy carriers).
[1] G.S. Grest et al., Phys. Rev. Lett. 29 (17), 1271 (1982).
[2] J.C. Li, A.I. Kolesnikov, Physica B 316-317, 493 (2002).

Contact: bel@niic.nsc.ru

28

X-ray Raman Spectroscopy Measurement for Detecting


Pressure-induced Dissociation of Water Molecules in Ice VII
Toshiaki Iitaka1, Hiroshi Fukui2, Zhi Li3,1, Nozomu Hiraoka4, Tetsuo Irifune5,6
1

Computational Astrophysics Laboratory, RIKEN, 2-1 Hirosawa, Wako,


Saitama 351-0198, Japan
2
Center for Novel Material Science under Multi-Extreme Conditions,
Graduate School of Material Science, University of Hyogo, Kamigori,
Hyogo 678-1297, Japan
3
School of Materials Science and Engineering, Hefei University of
Technology, Hefei 230009, Anhui, China
4
National Synchrotron Radiation Research Center, Hsinchu 30076, Taiwan
5
Geodynamics Research Center, Ehime University, 2-5 Bunkyo-cho,
Matsuyama, Ehime 790-8577, Japan
6
Earth-Life Science Institute, Tokyo Institute of Technology, Tokyo 152-8550,
Japan
According to X-ray diffraction (XRD) measurement[1], Ice VII is a crystalline phase
of water ice under high pressure being stable in a wide pressure range between 2.2
GPa and 60 GPa at room temperature. However, it exhibits many phenomena[2, 3]
originating from the complex proton dynamics, of which XRD provides very little
information. The neutron diffraction pattern of D 2 O ice was recently measured at
pressures up to 52 GPa by Guthrie et al. [4], who proposed an octahedral interstitial
proton model for ice at pressures above 13 GPa to account for the deviation of the
neutron diffraction pattern from that of ice VII. In this talk, the interstitial model is
theoretically and experimentally re-examined in terms of the interstitial occupancy
and X-ray Raman spectroscopy (XRS) spectra[5, 6]. The interstitial occupancy
calculated using first-principles molecular dynamics simulations was negligibly small
compared to that of the interstitial model. The oxygen K-edge spectra calculated for
the interstitial model exhibited two additional low-energy peaks originating from
water molecules and hydroxides that are interacting with interstitial protons,
respectively, whereas the experimentally measured spectra did not show these lowenergy peaks. These results suggest that the interstitial model cannot explain the XRS
spectra of ice at pressures above 13 GPa and that more precise structure
measurements and analyses[7] are necessary to reveal the peculiar nature[8] of the
pressure-induced transition.
[1]
E. Sugimura et al., Phys Rev B 77, 214103 (2008).
[2]
T. Okada et al., Sci. Rep. 4, 5778 (2014).
[3]
H. Hirai et al., High Pressure Research 34, 289 (2014).
[4]
M. Guthrie et al., Proc. Natl. Acad. Sci. U. S. A. 110, 10552 (2013).
[5]
H. Fukui et al., J. Chem. Phys. 127, 134502 (2007).
[6]
J. Y. Zhang, Z. R. Xiao, and J. L. Kuo, J. Chem. Phys. 132, 184506 (2010).
[7]
T. Hattori et al., Nuclear Instruments and Methods in Physics Research Section A:
Accelerators, Spectrometers, Detectors and Associated Equipment 780, 55 (2015).
[8]
T. Iitaka, Special Issue of The Review of High Pressure Science and Technology 24,
42 (2014).

Contact: tiitaka@riken.jp; URL:

http://www.iitaka.org/index_e.html

29

Atomic-Scale Modeling of the Mechanical and Dielectric


Properties of the Ultra-Low-k Nanoporous Silicate Glasses
Tsung-Ju Chen, Sheng-Shin Lin and Chin-Lung Kuo
Department of Materials Science and Engineering, National Taiwan University,
Taipei, Taiwan
Nanoporous silicate glasses have recently emerged as one of the most promising
candidates for the ultra-low-k inter-metal insulating materials of the next technology
node primarily due to their superior mechanical and dielectric properties as compared
with other low-k materials. At present, however, little is known about the details of
their molecular and topological structures as well as their influence on the mechanical
and dielectric properties of the insulating materials. In this study, we have performed
first principles calculations in conjunction with the classical force field modeling to
investigate the mechanical and dielectric properties of the organosilicates hybrid
glasses and the nanoporous amorphous silica for their potential application to the
interconnect technology in the advanced microelectronic devices. Based on our
newly developed computational approach to effectively generate realistic structure
models of the nanoporous silicate glasses, we have developed a detailed atomistic
understanding regarding the influence of the carbon content, porosity, and the
network connectivity on the mechanical and dielectric properties of the ultra-low-k
glasses. Our calculated results show that the organic cross-linking fragments do not
show any clear enhancement in the mechanical strength of the low-k glasses but
simply lower down the elastic moduli as the carbon content increases in the silicate
bond network. Our calculations further show that the mechanical strength of the
nanoporous silicate glasses appear to be a lot more dependent on the network
connectivity than on the porosity of the material matrix. In addition, we found that
different types of terminal groups (e.g. -CH3 or OH) may induce different degree of
porosity in the amorphous bond network primarily dependent on their interactions
with the constituent atoms in the material matrix, so as to change the mechanical
properties of the silicate glasses. On the other hand, our results also revealed that the
dielectric constants of the nanoporous silicate glasses are not necessarily lowered
down by the replacement of the O atoms with the methyl- or ethyl-bridging units.
Controlling the porosity of the material matrix seems to be a much more effective
way toward the synthesis of the ultra-low-k silicate glasses than by changing their
chemical composition.

Contact: chinlung@ntu.edu.tw

30

Elastic Properties of Dilute Si in Fe-Si Alloy


and Effect of Ni-Doping:
An Integrated Study Based on First-Principles
Ying Chen,1 Arkapol Saengdeejing,1 and Tetsuo Mohri2
1

School of Engineering, Tohoku University, Japan


Institute for Materials Research, Tohoku University, Sendai, Japan

Si-steel, a binary alloy with dilute Si in Fe-bcc, has a variety of applications due to its
excellent magnetic and mechanical properties. Some drastic change in mechanical
properties as Si concentration increasing to 9-10at.% has been intriguing since a long
time ago. To understand the mechanism of the Si concentration dependence of the
mechanical properties, especially a degradation of ductility as Si concentration is
beyond 9-10at.%, the electronic structure calculations incorporated with phonon
vibration effect and thermal electrons excitation are performed to Si-doped bcc-Fe
alloy up to 12.5at.%Si, the elastic properties such as bulk modulus, shear modulus
and elastic constants have been evaluated using the stress-strain method. The
calculations reproduced a non-monotonic change of the elastic properties with Si
concentration, found a ductile to brittle transition according to an empirical rule as Si
content increases beyond 9.4at.%, which is agree with the well known experimental
results. Analysis of density of states, magnetic moment revealed a relation of the
elastic properties to the magnetovolume effect of Fe-Si alloy at a low Si concentration
up to 8at.%. Further CVM calculation at finite temperature clarified the effect of the
D0 3 ordering on the recovery of elastic properties at Si concentrations being over
11at.%. Regard the Si concentration of 9-11at.% where the elastic properties decrease
sharply, we found that such a degradation is originated from the instability of density
of states at the Fermi energy, while this instability is the result of strong repulsive
interactions of certain Si-Fe-Si configurations in the Fe-Si alloy. Further calculations
with Ni-doping are conducted as considering an attractive feature of Ni in Fe-bcc,
which consequently achieved a recovery of all elastic properties. This is an
encouraging experience of tailing electronic structures by introducing specific atomic
configurations which adjusts bonding feature and the distribution of electrons toward
enhancing specific physical properties.

Contact: ying@rift.mech.tohoku.ac.jp

31

Single-Molecule Sequencing Using Nanopores and


Nanoelectrodes
Makusu Tsutsui1
1

The Institute of Scientifc and Industrial Research, Osaka University, Ibaraki,


Osaka 567-0047, Japan

Sequensing technologies for reading genetic information have been improving at


an ever increasing speed, the community is growing even faster than what Moores
law predicts, bringing a remarkable decrease in the cost to readout a human genome
[1]. In this perspect, various new techniques have been tested that aim to discriminate
the sequence of single-molecule DNA without labelling. Nanopore is a promising
candidate for this. It consists of a nanoscale hole in a thin membrane. By threading a
polynucleotide through the confined space in one direction, sequencing can be
accomplied by measuring the ionic current through the pore that is ecpected to
provide a characteristic fingerprint of each nucleotide via the ion exclusion effects of
the molecules. Though not yet sequencing, this method has proven to be quite useful
in detecting single-molecule DNA and investigating the fast translocation dynamics
[2].
Another single-molecule approach is sequencing by tunneling current. Here,
nanoelectrodess are used to address the electron transport through each nucleotides.
As the amount of current carried by individual molecules depends largely on the
molecular orbitals unique to them in the quantum regime, one can achieve sequencing
by measuring the tunneling current through each constituent nucleobases of DNA,
which has been first demonstrated by a scanning tunneling microscopy study in a
cryogenic vacuum.
In the presentation, recent efforts to realize a
sequencer
by
using
nanopores
and
nanoelectrodes will be reviewed. The potential
and challenges in these prospective systems will
also be discussed. In addition, the development
of electrode-embedded nanopores (Fig. 1) in our
group, which combines the nanopores and
nanoelectrodes to interogate the genome
sequence by tunneling current [3-4], will be
described.
Finally, novel nanoporebased
devices are intoduced that integrate additional
1. Schematic illustration of an
microstructures such as micropillars and Figure
electrode-embedded nanopore.
The
microchannels on a nanopore chip for two nanoelectrodes are used to detect
pretreating the analytes sampled from air.
the single-molecule current.
[1] NIH home page: https://www.genome.gov/sequencingcosts/
[2] M. Wanunu, Phys. Life Rev. 9, 125 158 (2012).
[3] J. Lagerqvist, M. Zwolak, and M. Di Ventra, Nano Lett. 6, 779-782 (2005).
[4] K. Yokota, M. Tsutsui, and M. Taniguchi, RSC Advances 4, 15886 (2014).
Contact: tsutsui@sanken.osaka-u.ac.jp

32

Spin Torque Effect in Spin-Filter Based Magnetic Tunnel


Junction
Yu-Hui Tang()1 , Fa-Chieh Chu()1 , and Nicholas Kioussis2
1
2

Department of Physics, National Central University, Jhong-Li, Taiwan


Department of Physics, California State University, Northridge, CA, USA

Recent discoveries in the ferromagnet/insulator/ferromagnet (FM/I/FM) magnetic


tunnel junctions (MTJs) have demonstrated that the relative orientation of the two FM
electrodes can be either altered by an external magnetic field, i.e. the tunneling
magnetoresistance (TMR) effect, or controlled by a spin-polarized current, i.e. the
current-induced magnetization reversal via the spin transfer torque (STT) effect. The
spin-transfer, || , and field-like, , components of the STT originate from different
components of the spin current accumulated at the FM/I interface and can be
expressed in terms of the interplay of spin current densities and of the nonequilibrium interlayer exchange couplings [1], respectively, solely in collinear
configurations.
The insulator in conventional FM/I/FM MTJs plays only a passive role in the spinpolarized transport. The evolution beyond passive components has broadened the
quest for multifunctional spintronic devices consisting of spin-filter (SF) barriers [2],
which exploits the separation of the barrier heights of the two spin channels that can
be in turn tuned via an external magnetic field.
In this study, the tight binding calculations and the non-equilibrium Green's
function formalism is employed to study the effect of the SF-barrier magnetization on
the bias behavior of both components of STT in noncollinear FM/I/SF/I/FM junctions.
We predict a giant in contrast to conventional FM/I/FM junctions, which has
linear bias dependence, is independent of the SF thickness, and has sign reversal via
magnetic field switching. Our results suggest that the novel dual manipulation of
either by a magnetic field or bias can be employed for reading or writing
processes, respectively, in the next-generation field-like-spin-torque MRAM (FLSTMRAMs). Finally, our newly derived general expressions of noncollinear || and
allows the efficient calculation of the STT from collinear ab initio electronic structure
calculations [3,4]. (Contract No. NSC 102-2112-M-008-004-MY3)
[1]
[2]
[3]
[4]

Y. H. Tang et al., Phys. Rev. B 81, 054437 (2010).


T. S. Santos and J. S. Moodera, Phys. Today 63, 46 (2010).
X. Jia, K. Xia, Y. Ke, and H. Guo, Phys. Rev. B 84, 014401 (2011).
Y. H. Tang and F. C. Chu, J. Appl. Phys. 117, 093901 (2015).

Contact: yhtang@cc.ncu.edu.tw

33

Spin-polarized Transport through Single-molecule Magnetic


Junctions
Chuang-Han Hsu,1,2 Yu-Hsun Chu,2 Chao-Cheng Kaun,1 and Minn-Tsong Lin2
1

Research Center for Applied Sciences, Academia Sinica, Taipei, Taiwan


2
Department of Physics, National Taiwan University, Taipei, Taiwan

We investigate spin-polarized (SP) electronic transport properties and hybrid states of


a single manganese phthalocyanine (MnPc) molecule adsorbed on a Co nanoisland,
with the SP scanning tunneling microscopy measurements and the first-principles
calculations. Our analyses show that the MnPc molecule can pin the Co surface state
to the Fermi level, forming hybrid stationary spin resonance states which, with an
antiparallel-magnetization tip, give a resonant SP conductance peak. Our calculations
further reveal that as the tip approaches the molecule, electronic and magnetic
couplings in the junction are tuned as the Zener indirect exchange coupling becomes
prominent, which switches the conduction carriers from s to d electrons and leads to
the tailored magnetic moments and magnetoresistance. [1]

[1] C.-H. Hsu, Y.-H. Chu, C.-I Lu, P.-J. Hsu, S.-W. Chen, W.-J. Hsueh, C.-C.
Kaun, and M.-T. Lin, J. Phys. Chem. C 119, 3374 (2015).

Contact: kauncc@gate.sinica.edu.tw

34

Local Heating and Cooling criterion in Nanoscale Systems


Ilias Amanatidis, Yu-Chang Chen
National Chiao Tung University, Hsinchu, Taiwan
We study at finite bias voltage the conditions under which local cooling and heating
exist in the case of electron-phonon interactions. Our calculations are based on a
simple model, coupled to a single phonon that provides us a microscopic and detailed
picture of the heating mechanism generated in nanoscale systems. We show that the
electron-phonon coupling constant introduces an interplay between two mechanisms
that of local cooling and that of local heating. More specific, assuming the simplest
form for the coupling constant, an energy linear dependence local heating occurs
when its slope is positive that is that the rate of absorption energy by the ion atom is
smaller than the rate of its emission while local cooling occurs when the slope of the
electron-phonon coupling constant is negative, that is that the rate of the phonon
absorption is larger than the rate of the phonon energy emission.
Contact: eliasamanatidis1@hotmail.com

35

Computational Investigation of Electron Injection of Squaraine


Dye-Sensitized Solar Cells
Hui-Hsu Gavin Tsai
Department of Chemistry, National Central University, Jhongli District, Taoyuan City, Taiwan
E-mail: hhtsai@cc.ncu.edu.tw
Because the intense absorptions of squaraine (SQ) dyes in the red/near-infrared spectral
regions closely match the spectral response of sunlight, SQ dyes have promising applications
in dye-sensitized solar cells (DSCs) as well as in organic photovoltaic cells. In this study, we
employed density functional theory (DFT) and time-dependent DFT to investigate the
photophysical properties of seven reported SQ-derived dyes adsorbed on a (TiO 2 ) 38 cluster
having an anatase (101) surface, as a model for corresponding DSCs. In particular, we
calculated the proportion of electron density distribution and the alignment of excited-state
energy levels of SQ(TiO 2 ) 38 upon photoexcitation, which allow us to investigate their
electron injection mechanisms. We found that the calculated electron density injected into
(TiO 2 ) 38 cluster and the driving force of electron injection are highly correlated with
experimentally observed short-circuit current (Jsc).
JD10 and YR6 with the highest Jsc values (> 14.5 mA/cm2), their transitions have large
proportions of electron density distributed to TiO 2 upon excitation (> 45%) and have driving
force for excited-state electron injection. In contrast, electron injection from SQ12, SQ2, and
SQ4 dyes upon excitation followed the indirect mechanism of electron injection; these dyes
have negligible proportion of electron density transferred into TiO 2 (< 5%). Furthermore,
SQ2 and SQ4 have no additional driving force for excited-state electron injection. SQ12, SQ2,
and SQ4 based devices indeed have the lowest J sc values (~ 6 mA/cm2) than those of other
studied dyes. SQ01 and SQ02 have similar lowest driving forces as those of JD10 and YR6;
however, SQ01 and SQ02 have smaller electron density delocalized into the TiO 2 moiety (~
20%) upon excitation than those of JD10 and YR6. Experiments show SQ01 and SQ02 based
devices generate J sc values lower than those of JD10 and YR6 and are higher than those of
SQ12, SQ2, and SQ4. Our calculations are well compatible with experimentally observed Jsc.

[1] Tsai, H. H. G.; Tan, C. J.; Tseng, W. H. J. Phys. Chem. C 2015, 119, 4431.

36

Metal-Free Sensitizers for Dye-Sensitized Solar Cells:


Structure/Performance Correlation
Jiann T. Lin,1 Jen-Shyang Ni,1 Hsien-Hsin Chou,1 Sumit Chaurasia,1 Yung-Sheng
Yen,1 Jian-Hao You,1,2 Chang-Tze Lee,1,2 Chih-Yu Hsu,1 Ying-Chan Hsu,1 Marappan
Velusamy,1 and Chao-Pin Hsu1
1

Institute of Chemistry, Academia Sinica, Taipei 11529, Taiwan


Department of Chemistry, National Central University, Chungli 320, Taiwan

Several series of metal-free dyes with a structural motif, DA'A (D = donor; =


conjugated spacer; A' = acceptor; A = acceptor/anchor, were synthesized and used as the
sensitizers of dye-sensitized solar cells (DSSCs). Incorporation of the electronwithdrawing second acceptor A' in the conjugated spacer leads to bathochromic shift
of the intramolecular charge transfer (ICT) band. However, significant charge
trapping at the strong second acceptor may lead to inefficient electron injection and
jeopardize the cell performance. Balance of light-harvestng and charge-trapping can
be achieved via tuning of the A' entity. From 4,7-linked [1,2,5]benzothiazole to 4,7-linked
2-H-benzotriazole, charge-trapping is largely alleviated at the expense of light-harvesting. On
the contrary, from 4,7-linked [1,2,5]benzothiazole to 4,7-linked pyridal[2,1,3]benzothiazole,
the ICT band is red shifted at the expense of charge trapping. From 4,7-linked
pyridal[2,1,3]benzothiazole to 4,7-linked 2H-[1,2,3]triazolo[4,5-c]pyridine, there is

hypsochromic shift of the ICT band and more serious charge trapping. The cell
efficiency of the 2H-[1,2,3]triazolo[4,5-c]pyridine derived sensitizer is nearly one order
better than that of the [1,2,5]benzothiazole derived sensitizer. When an electron-rich
entity and an electron-deficient entity are fused as a rigid segment A' such as
dithieno[3',2':3,4;2'',3'':5,6]benzo[1,2-c]-furazan and dithieno[3,2-f:2',3'-h]quinoxaline,
the best cell efficiency reaches 7.33% and 8.41%, respectively. No serious chargetrapping was found in these two cases. [1], [2], [3], [4]

[1] Velusamy, M.; Justin Thomas, K. R.; Lin, J. T.; Hsu, Y.-C.; Ho, K.-C., Org.
Lett. 7, 1899, (2005).
[2] Yen, Y.-S.; Lee, C.-T.; Hsu, C.-Y.; Chou, H.-H.; Chen, Y.-C.; Lin, J. T.,
Chem. Asian J. 8, 809 (2013).
[3] Chaurasia, S.; Hung, W.-I.; Chou, H.-H.; J. T. Lin, J. T., Org. Lett. 16, 3052
(2014).
[4] Ni, J.-S.; Kao, W.-S.; Chou, H.-J.; Lin, J. T., ChemSusChem 8, DOI:
10.1002/cssc.201 (2015).

Contact: jtlin@gate.sinica.edu.tw

37

Polyfused Aromatics as Charge Transport Materials in


Field-Effect Transistor Applications: A Structure-Property
Correlation Study
Yu-Tai Tao,1,2
1

Department of Chemistry, National Tsing-Hua University, Hsin-chu, Taiwan


2
Institute of Chemistry, Academia Sinica, Taipei, Taiwan

Organic field-effect transistor (OFET) is attracting much attention due to its role in
the organic electronics. Polyfused aromatic compounds are widely used as the charge
conducting channel materials in the fabrication of organic field-effect transistors. The
charge transport in organic materials depends on the electronic coupling between the
molecules, as well as the reorganization energy of the molecule itself. The electronic
coupling is highly sensitive to the exact crystal packing of the molecules. In this talk,
we will present our efforts of systematically examining the effect of molecular
framework and its substitution on the field-effect charge mobility, as extracted from
single crystal field-effect transistors (SCFET) fabricated with a series of polyfused
aromatics. Theoretical calculation was also carried out in an effort to obtain more
insights to the structure-property correlation. A contorted tetrabenzocoronene
derivatives (TBCs, 1) and a planar dibenzobistetracene derivatives (BDDTs, 2) will
be discussed in detail.

[1]

Kuo, C. H., Huang, D. C.; Peng, W. T.; Goto, K., Chao, I.; Tao, Y. T.
J. Mater. Chem. C. 2, 3928 (2014).

Contact: ytt@gate.sinica.edu.tw

38

Ab Initio Calculation of Plasmon Excitations in Graphene


and Nonlinear Optical Properties of Transition Metal
Dichalcogenide Monolayers
Guang-Yu Guo ()1
1

Department of Physics, National Taiwan University, Taipei 10617, Taiwan

Graphene, a two-dimensional material with carbon atoms arranged in a single-layer


honeycomb lattice possessing an unusual band structure with a linear spectrum, hosts
two-dimensional (2D) Dirac fermions. It provides a great opportunity to investigate
novel phenomena in low-dimensional Dirac fermion systems. Furthermore, the easy
manipulation of the Fermi level by an applied gate voltage also makes graphene an
excellent candidate for technological applications. The current interest in graphene
has also stimulated research efforts to fabricate other 2D materials such as
monolayers of group IV elements and transition metal dichalcogenides. These
emergent 2D materials could exhibit a number of intriguing properties such as direct
optical band gaps, spin-valley coupling, piezoelectric and nonlinear optical responses
that the corresponding bulk materials do not have. Thus, they have promising
applications such as novel types of transistors, optoelectronic and spin transport
devices. We have recently performed ab initio calculations to provide a theoretical
understanding of the fundamental properties of these emergent materials and also to
assess their application potentials. In this talk, I will focus on the plasmon excitations
in graphene [1] and second-order nonlinear optical properties of transition metal
dichalcogenide monolayers [2].
[1] S. C. Liou, C.-S. Shie, C. H. Chen, R. Breitwieser, W. W. Pai, G. Y. Guo and M.W. Chu, -plasmon dispersion in free-standing graphene momentum-resolved
electron-loss spectroscopy, Phys. Rev. B 91, 045418 (2015).
[2] C.-Y. Wang and G. Y. Guo, Nonlinear Optical Properties of Transition Metal
Dichalcogenide MX2 (M = Mo, W; X = S, Se) Monolayers and Trilayers from
First-principles Calculations, arXiv:1409.0937v2 (2014).

Contact: gyguo@phys.ntu.edu.tw

39

Magnetic ordering on edges of topological insulators


Jisoon Ihm,1 Yea-Lee Lee,1 Hee Chul Park2, and Young-Woo Son2
1

Department of Physics and Astronomy, Center for Theoretical Physics, Seoul


National University, Seoul 151-747, Korea
2
Korea Institute for Advanced Study, Seoul 130-722, Korea

A topological insulator (TI) hosts the topologically protected metallic surface states
on its boundaries between inner insulating bulk and outer vacuum, and manipulations
of its exotic states lead to various interesting phenomena such as quantum anomalous
Hall effects and topological magneto-electric couplings. Most studies hitherto have
been limited to a specific facet of three-dimensional TI crystals without considering
the existence of other surface states on adjacent facets. However, topological surface
states of a single TI crystal can exist on all the surfaces with different crystal
orientations enclosing the crystal, and mutual interactions among those contiguous to
each other through edges have not yet been examined well. First-principles electronic
structure calculations as well as the theory of the axion electrodynamics indicate that
a net magnetic ordering should be induced on edges between different facets of the
three-dimensional TI crystal. In a prototypical TI such as Bi 2 Se 3 , the difference in the
work function between different crystal-face orientations generates a built-in electric
field around facet edges so that the lines of effective magnetic dipoles accumulate at
those edges for a given broken time-reversal symmetry. The predicted magnetic
ordering depending only on the work function differences between facets would be a
unique manifestation of the axion electrodynamics in real solids and suggests a route
to reveal novel electric and magnetic properties of macroscopic topological edge
states of a TI.

Contact: jihm@snu.ac.kr, hand@kias.re.kr

40

The Topology of Ideal Conduction


B. Hetnyi
Department of Physics, Bilkent University, Ankara, Turkey
One of the most interesting recent discoveries in physics is topological
insulation[1]. Topological insulation can be viewed as an extension of the quantum
Hall effect.
The Hall conductance in a quantum system is characterized by a
topological invariant[2], which arises upon integrating around the Brillouin zone of a
two-dimensional system. Nontrivial behavior results from application of an external
magnetic field but it can also arise from magnetic impurities without an external
field[3]. Similarly, topological insulators are characterized by topological invariants
which display nontrivial behavior in particular cases, for example in spin-orbit
coupled systems. A common feature of topological insulators and quantum Hall
systems is that they display particular behavior at their boundaries, where the
topological invariant changes from a trivial to a non-trivial value (principle of bulkboundary correspondence[4]). In this talk an overview of the quantum Hall effect and
topological insulation will be given. Subsequently it will be shown that ideal
conduction is also a topological physical effect[5]. The topological invariant
associated with the Drude weight will be derived. This invariant is similar in form to
the Hall conductance, however it arises upon integrating around a rectangle one of
whose sides is the crystal momentum in some direction, the other being the total
position in the same direction. It will be argued that the Drude weight, as well as
related transport quantities[6,7] (Meissner weight in superconductors, superfluid
weight in superfluid 4He) can in principle exhibit quantization both integer and
fractional. Indeed, superconductors exhibit flux quantization in cavities, superfluids
give rise to vortex quantization. If time permits then also the analog of the bulkboundary correspondence principle for ideal conduction and its relation to the
Meissner effect will be discussed[8].
[1] C.L. Kane and E.J. Mele, Phys. Rev. Lett. 95, 146802 (2005).
[2] D.J. Thouless, M. Kohmoto, M.P. Nightingale, and M. den Nijs, Phys. Rev.
[3]
[4]
[5]
[6]
[7]
[8]

Lett. 49, 405 (1982).


F.D.M. Haldane, Phys. Rev. Lett. 61 2015 (1988).
B.I. Halperin, Phys. Rev. B, 25 2185 (1982).
B. Hetnyi, Phys. Rev. B, 87 235123 (2013).
B. Hetnyi, J. Phys. Soc. Japan, 83 034711 (2014).
B. Hetnyi, arXiv:1406.0712.
M. Yahyavi and B. Hetnyi, in preparation.

Contact: hetenyi@fen.bilkent.edu.tr

41

Inverse Design and Computational Studies of Novel Solar


Energy Materials
X.G. Gong
Key Lab for Computational Physical Sciences (MOE), Department of Physics, Fudan University

Shanghai,200433, China
email: xggong@fudan.edu.cn
With the rapid development of the modern computational techniques,
computational studies on the condensed matter, including understanding physical
mechanism, simulating specific dynamics processes and designing desired materials,
have played a more and more important role. A direct design of materials with desired
properties, so-called inverse deign, has been a long-standing dream in computational
materials science.
In this talk, I will first show our newly developed algorithm for the inverse deign
of materials (IM2ODE: Inverse Design of Materials by Multi-Objective Differential
Evolution). As an example, I will demonstrate how we can obtain a direct-gap
elemental semiconductor phase that is proper for the solar energy absorbers with this
package.
The band offset is a fundmental property in designing of solar cell. However, both
the theoretical prediction and experimental determination are not trival. I will talk
about our new algorithm on the calculation of band offset, comparison shows that the
new algorithm has obvious advantages over previous methods.

42

Thermoelectric properties in atomic/molecular junctions


from first principles
Yu-Chang Chen
Department of Electrophysic, National Chiao Tung University, Hsinchu,
TAIWAN
Thermoelectric nanojunctions for use in the development of new forms of
energy-conversion devices at the nanoscale have attracted rapidly growing attention.
Thermoelectric nanojunctions consist of a nano-structured object sandwiched
between source-drain electrodes. As the Seebeck coefficients are relevant not only to
the magnitude but also to the slope of density of states (DOSs), it is of key importance
to investigate the details of electronic structures in thermoelectric nanojunctions.
Electronic structures offered by sized reduction thereby provide new opportunities
and challenges for exploring new forms of nanoscale renewable energy system. Due
to the relatively small sizes of junctions, the nature of electron transport are
characterized by coherent wave functions. To calculate the wave functions in
atomic/molecular junctions, density-functional theory (DFT) combined with
Lippmann-Schwinger equation (LS) is applied to investigate non-equilibrium electron
transport and thermoelectric properties. Firstly, we will briefly present an introduction
for DFT+LS theory for nanoscale junctions formed by atoms/molecules sandwiched
between bimetallic electrodes. We then focus on how we apply LS+DFT to
investigate the Seebeck coefficients in atomic/molecular junctions from firstprinciples approaches [1-4]. To gain further insight into the quantum transport of
electrons and energy under nonequilibrium conditions, we investigate effects of
electron-vibration interactions on the Seebeck coefficient and the figure of merit ZT
[5,6]. We also propose several atomic-scale thermoelectric devices, such as nanorefrigerators [7], power generators, and self-powered atomistic transistor [8].

1. Y. S. Liu, and Y.-C. Chen, Seebeck coefficient of thermoelectric molecular junctions: Firstprinciples calculations, Phys. Rev. B 79, 193101 (2009).
2. Y. S. Liu, Yi-Ren Liu, and Y.-C. Chen, Thermoelectric efficiency in nanojunctions: A comparison
between atomic junctions and molecular junctions, ACS Nano 3, 3497 (2009).
3. B. C. Hsu, H. T. Yao, W. L. W. L. Liu, and Y.-C. Chen, Oscillatory and sign-alternating behaviors
of the Seebeck coefficients in carbon monatomic junctions, Phys. Rev. B 88, 115429 (2013).
4. B. C. Hsu, C. Y. Lin, Y. S. Hsieh, and Y.-C. Chen, Tailoring thermopower of single-molecular
junctions by temperature-induced surface reconstruction, Appl. Phys. Lett. 101, 243103 (2012).
5. B. C. Hsu, Y. S. Liu, S. H. Lin, and Y.-C. Chen, Seebeck coefficients in nanoscale junctions:
Effects of electron-vibration scattering and local heating. Phys. Rev. B 83, 041404(R) (2011).
6. B. C. Hsu, C. W.Chiang, and Y.-C. Chen, Effect of Electron-Vibration Interactions on the
Thermoelectric Efficiency of Molecular Junctions, Nanotechnology 23, 275401 (2012)
7. Y. S. Liu, B. C. Hsu, and Y.-C. Chen, Effect of thermoelectric cooling in nanoscale junctions, J.
Phys. Chem. C 115, 6111 (2011).
8. Y. S. Liu, H. T. Yao, and Y.-C. Chen, Atomic-scale field-effect transistor as a thermoelectric
power generator and self-powered device, J. Phys. Chem. C 115, 14988 (2011).

Email: yuchangchen@mail.nctu.edu.tw
Website: http://www.ep.nctu.edu.tw/ycchen

43

First Principles Study of Redox Reactions for


Energy Storage and Conversion
Dr. Patrick Sit
School of Energy and Environment, City University of Hong Kong
Density-functional techniques have become powerful tools that provide atomic-scale
understanding and realistic prediction of material properties, thanks to the ever-increasing
computer power and the development of more efficient and accurate methodologies. In this
talk, I will highlight examples of redox reactions in nanoscale systems important in energy
storage and conversion. In particular, I will discuss the recent study of the cobalt molecular
complexes for hydrogen production. Focus will be placed on the effects of the solvent
structure and the solvent-catalyst interaction on the reaction mechanisms. Moreover,
investigation of transition-metal-containing heterogeneous catalysts for hydrogen evolution
and CO oxidation will also be discussed.

44

Dynamics and Anomalous diffusions in the liquid crystals


inverse hexagonal phase: a molecular dynamics simulation
study
Hockseng Nguan and Rauzah Hashim
Department of Chemistry, University of Malaya, Kuala Lumpur, Malaysia

Inverse hexagonal phase (H II ) is one of the most common curve phases in lipidic
liquid crystals. In the H II phases, molecules are confined in two dimensions which
orthogonal to its columnar axis. By using the H II phase formed glycolipids as our
study case and the molecular dynamics simulations methods, we study the motion of
the water and glycolipids molecules in the 2-D confined system. In the H II phase,
water molecules are inside the nano sized channel surrounded by sugar head group of
the glycolipids. This essentially a representative system for water molecules
occupying a nonionic hydrophilic nano channel, where the behaviors of water are
different from when it was in bulk. In recent experiment by Peneloza et al. [1], the
diffusion of water in H II of nonionic lipids (hexaethylene glycol) are found to be
anomalous compared to other lamellar phase of the same system, although in both
cases, water is in nano-sized confined. Through our computer simulations study of
H II phase [2], we able to provide the explanation the observation in the experiment.
Furthermore, we have also investigated rotational diffusions and hydrogen bonding of
confined waters which help in understanding the hydration in the H II phase. On the
other hand, the diffusion of the lipid molecules in the H II phase are separated into 1-D
linear and 2-D circular, where the directions are orthogonal to each other. Through
our computer simulations of system with different hydration, these two diffusions
were studied and compared.

[1] Peneloza et al., Phys. Chem. Chem. Phys., 14(15), 5247 (2012)
[2] Hock-Seng Nguan, Sara Ahmadi and Rauzah Hashim, Phys. Chem. Chem.
Phys., 16, 324 (2014)

Contact: E-mail: nguanhs@um.edu.my

45

Theoretical Investigation of Using Silsesquioxane


Frameworks for Hydrogen Storage System
Yun-Wen Chen,1 Amol Deshmukh,1 and Jer-Lai Kuo1
1

Institute of Atomic and Molecular Sciences, Academia Sinica, Taipei, Taiwan

Finding more compact and feasible hydrogen storage systems is still a developing
field for the coming hydrogen economy. [1] Department of Energy (DOE), US has
announced the criteria of applicable hydrogen storage system. [2] The two main
targets need to be satisfied are gravimetric density higher than 6 wt% and volumetric
density higher than 45 g/L (targets by 2010). Several porous materials are recently
proposed for hydrogen storage application with characters of large contact area and
weight/volume ratio. [3] However, finding the suitable material meeting all criteria is
hard; hence, the game of improving storage capacity and delivery efficiency is still
ongoing in order to build a hydrogen economy with cheap enough resources.
In this study, we investigate the possibility of using silsesquioxane frameworks for
hydrogen storage via density functional theory calculations. With some metal
decorations, silsesquioxane frameworks show very plausible operational ranges (near
ambient conditions) for hydrogen gas delivery. Meanwhile, the gravimetric density
can go up as high as 7 wt% and volumetric density much higher than 45 g/L. We also
investigate the effect of stretching and magnetizations of framework to the adsorption
of hydrogen gas.

[1] P. Jena, J. Phys. Chem. Lett. 2, 206 (2011). I. P. Jain, Int. J. Hydrogen Energy
34, 7368 (2009).
[2] http://energy.gov/eere/fuelcells/downloads/explanations-freedomcardoehydrogen-storage-technical-targets
[3] E. Klontzas, A. Mavrandonakis, E. Tylianakis, and G. E. Froudakis, Nano Lett.
8, 1572 (2008). X.-D. Li, H. Zhang, Y. Miyamoto, Y.-J. Tang, C.-Y. Wang,
Struct. Chem. 25, 177 (2014).
Contact: ywchen@pub.iams.sinica.edu.tw

46

First-principles study of stability of Cu in the Nd-rich and


Nd Oxide phases of Nd-Fe-B permanent magnet
A. Saengdeejing1, Y. Chen1, M. Matsuura2, S. Sugimoto2
1

Fracture and Reliability Research Institute, Graduate School of Engineering,


Tohoku University, Sendai, Japan
2
Department of Materials Science, Graduate School of Engineering, Tohoku
University, Sendai, Japan

In the Nd-Fe-B permanent magnet materials, existing of small amount of copper can
increases the coercivity which is very important property of the magnet. In order to
understand the microscopic mechanism of the effect of opper on the properties of the
Nd-Fe-B magnet, first-principles calculations based on density functional theory
coupled with cluster expansion method are performed to investigate the phase
stability in Cu-doped Nd and Nd-O system. Vienna Ab-initio Simulation Package
(VASP) with projector augmented-wave method (PAW) and generalized gradient
approximation (GGA) that described the exchange and correlation energies are used.
Cluster expansion is performed using Alloy Theoretic Automated Toolkit (ATAT)[1].
Table 1 shows the formation energies of several Cu-doped structures compare with
their perfect structures. Although, the formation energy of Cu in Nd-dhcp structure is
positive but still relatively small which indicates that there is a possibility of Cu
solubility in Nd-dhcp phase. The formation energy of Cu in NdO-ZnS structure is the
only case that lowers than un-doped structure. Thus, it is also possible to have Cu
soluble in NdO-ZnS structure.
Figure 1 shows the result of (Nd,Cu)O cluster expansion in ZnS structure which
confirm that mixing between Cu and Nd in this structure is more stable than NdO or
CuO in ZnS structure.
[1] A. van de Walle, M. Asta, G. Ceder, CALPHAD: Comput. Coupling of Phase
Diagrams and Thermochem. 26, 539 (2002).
Table 1: Formation energy of Cu-doped

Structures
Nd-dhcp
NdO-B1
NdO-ZnS
Nd2O3-hP5
Nd2O3-cl80

Formation energy, eV/atom


Perfect
Cu-doped
0
-2.699
-2.496
-3.306
(-3.76*)
-3.299
8a
24d

0.037
-2.575
-2.565
-3.063

-3.085
-3.080
Figure 1: Cluster expansion result

Contact: aksaengdeejing@rift.mech.tohoku.ac.jp

47

Adiabatic treatment for vibrational predissociation of water


dimers with channel interactions
H. Mineo*1, S.H. Lin2, and Y. Fujimura2, 3
1 Institute of Atomic and Molecular Science, Academia Sinica, Taipei 115, Taiwan,
2 Department of Applied Chemistry, Institute of Molecular Science and Center for Interdisciplinary Molecular Science, National Chiao
Tung University, Hsinchu 30010, Taiwan
3 Department of Chemistry, Tohoku University, Sendai, Japan

Infrared-induced vibrational predissociation (VPD) of water is considered to be an important


reaction dynamics of water, but due to the complicated structure of the water cluster, direct
measurement of the IR induced VPD rate constant is difficult. Therefore, the water dimer is
expected to play an important role as a smallest water cluster to study the dynamics of VPD.
However, the vibrational predissociation mechanism of hydrogen bonding water cluster is less
understood at present stage.
The vibrational modes of the donor and accepter H 2 O units of water dimer were grouped to highfrequency degrees of freedom which are localized in the donor or acceptor units, and the
intermolecular modes were grouped to the low frequency-degrees of freedom in the adiabatic
description.
We consider three VPD processes of water dimers (H 2 O) 2 and (D 2 O) 2 from the initial channel of
the one-quantum excitation of the totally symmetric OH (OD) vibration in the donor water unit, (1 0
0) d + (0 0 0) a to the two open channels of the bending-mode one-quantum excitation in the donor and
acceptor water units, (0 1 0) d + (0 0 0) a and (0 0 0) d + (0 1 0) a , respectively, and the other is to the
open channel of the ground-state water dimer, (0 0 0) d + (0 0 0) a .
The corresponding VPD rate constants were calculated in the non-Condon scheme beyond the
so-called Condon approximation. The VPD is induced by the breakdown of the vibrational adiabatic
approximation and the two types of the nonadiabatic coupling matrix elements are involved: the VPD
induced by the low-frequency dissociation mode and VPD of the other one through the channel
interactions induced by the low-frequency vibrational modes. The channel interactions in the initial
and/or final stages were taken into account.
The calculated VPD rates of the (H 2 O) 2 are slow compared with those of the (D 2 O) 2 for the case in
which the channel interactions were omitted, while these are comparable order for the case in which
the channel interactions were taken into account. The results are also compared with the results of the
quasi-classical calculations and experimental results [1, 2].

(0,1,0)d +(0,0,0)a

(0,0,0)d +(0,1,0)a

(1,0,0)d +(0,0,0)a

(0,0,0)d +(0,0,0)a

Figure 1. Vibrational VPD of water dimers from the initial channel (1 0 0)d + (0 0 0)a to the final
channels: (0 1 0)d + (0 0 0)a, (0 0 0)d + (0 1 0)a and (0 0 0)d + (0 0 0)a, are depicted.
[1] L. C. Chng, A. K. Samanta, G. Czak, J. M. Bow-man, H. Reisler, 2012 J. Am. Chem. Soc.
134 15430.
[2] G. Czak, Y. Wang, and J. M. Bowman, 2011 J.Chem. Phys. 135, 151102.

Contact: mineo@gate.sinica.edu.tw

48

A Theoretical Investigation of Surface-enhanced SumFrequency Generation


Y.L.Yeh1, J.Lei2, S. Y. Chen3, A.H.H. Chang3, C.K. Lin4 , Rong Xing He2 and
S.H. Lin1,5
1

Department of Applied Chemistry, National Chiao-Tung University, Hsin-Chu,


Taiwan
2
College of Chemistry and Chemical Engineering, Southwest University, Chong
Qing, ROC
3
Department of Chemistry, National Tung-Hwa University, Hwa-Lien, Taiwan
4
National Taiwan University, Taipei, Taiwan
5
e. Institute of Atomic and Molecular Sciences, Academia Sinica, Taipei, Taiwan

Following the surface enhanced Raman scattering (SERS), we shall investigate the
possibility of observing surface-enhanced sum-frequency generation (SESFG), which
refers to the transformation of ordinary vibrational SFG (i.e. singly resonant) into
SESFG. Two mechanisms of SESFG will be studied; one is due to the transformation
of singly-resonant vibrational SFG into doubly resonant vibrational SFG (that is, both
vibrationally resonant and Raman-scattering resonant) and the other is due to the
enhancement of the polarizability in addition to the original vibrational resonance in
vibrational SFG.

Contact: sheng@mail.nctu.edu.tw, yehyl@gate.sinica.edu.tw

49

New Conductive Imidazole-derived Salt for Lithium-ion


Battery Electrolytes: a DFT study
Ermias Girma Leggesse and Jyh-Chiang Jiang
Department of Chemical Engineering, National Taiwan University of Science and
Technology, Taipei, 106, Taiwan, R.O.C
LiPF 6 , which is the most widely used electrolyte salt in lithium ion batteries, is
reported to have series problems that may lead to performance and safety issues.[1] In
order to solve its problems, researches have focused on designing new lithium salts
which have thermal and electrochemical stability, high ionic conductivity and easy
synthesis route.[2-5] In this work, we report designing of an alternative salt derived
from bis(trifluoroborane)imidazolide (LiIm(BF 3 ) 2 ) by employing density functional
theory (DFT) calculations. New anion structures were generated by considering
substitution at the C5 position with electron withdrawing groups (-F, -CF 3 , -SO 3 H
and -NO 2 ) and electron donating groups (-NH 2 , -OCH 3 and CH 3 ). By using the
optimized anion structures, random lithium ion-pair configurations (around 130
structures for each) were generated and optimized to identify the most stable
configurations. The effects of different substituents were investigated with respect to
ion dissociation energies, anion oxidative stability, and aromaticity of the molecule.
Based on our calculations, we have found that, ion dissociation energies and intrinsic
oxidative potentials of anions largely affected by the type of substituents introduced
on the parent structure. Compared to -PF 6 and LiIm(BF 3 ) 2 , substituted -CF 3 and NO 2 substituted anions showed an increase in anion oxidation stability. Since, BF 3
occupies the strong Lewis basic sites of the imidazole ring, the parent structure itself
exhibit a charge delocalization over the aromatic ring, which results in a weak
coordinating ability with Li+. With the exception of F, -CF 3 and CH 3 , further
introduction of substituents on C5 position led to a much lower cationanion
interaction.
Among
the
possible
anions
studied,
5-nitrobis(trifluoroborane)imidazolide, with oxidation potentials > 5.7 V vs. Li+/Li , can be
considered as a good candidates for high voltage Li-ion battery applications.
Moreover, we have also found that the ion-pair dissociation energy, and anion
stability of the selected salt are much improved compared to experimentally reported
LiIm(BF 3 ) 2 and LiPF 6 .
[1] Xu, K. Chemical Reviews 104, 4303-4418(2004)
[2] Angenendt, K. & Johansson, P. J Phys Chem B 115, 7808-7813 (2011)
[3] Johansson, P. & Jacobsson, P. J Power Sources 153, 336-344 (2006)
[4] Jonsson, E. & Johansson, P. Phys Chem Chem Phys 14,10774-10779 (2012)
[5] Scheers, J. et al. Phys Chem Chem Phys 13, 11136-11147 (2011)

Contact: jcjiang@mail.ntust.edu.tw

50

Predicting New Phases of Solid Methanol


Tzu-Jen Lin and Jer-Lai Kuo
Institute of Atomic and Molecular Sciences, Academia Sinica, Taipei City, Taiwan

Both chain and ring conformations exist in liquid methanol which is confirmed by
experiment studies. Nevertheless, three known phases in solid methanol, alpha, beta,
and gamma, are categorized in infinite hydrogen bond chains with slightly different
configurations to each other. Recent dielectric properties measurement suggests that
there could be a new phase for solid methanol but the crystal structure is unknown.
An interesting question can be raised based on this finding. Could it be ring structure
or something else? In this study, density functional theory (DFT) with various
dispersion corrections and generalized energy-based fragment approach (GEBF) were
used and combined with random search technique to predict new phase of solid
methanol. We surprisingly find there are many kinds of ring and helix structures
having comparable energies to infinite strained hydrogen bond structures between 0
to 5 GPa by preliminary analysis. This finding could explain why methanol is hard to
crystalize under pressures.

Contact: jlkuo@pub.iams.sinica.edu.tw

51

Modeling of Composition and Formation Conditions of


Double Hydrates of Tetrafluoromethane or Nitrous Oxide
with methane
Bozhko Yu Yu,1,2 Subbotin O S,1,2 and Belosludov V R1,2
1

Nikolaev Institute of Inorganic Chemistry, SB RAS, Novosibirk, Russia


Kutateladze Institute of Thermophysics, SB RAS, Novosibirsk, Russia

Clathrate hydrates, so called gas hydrates, are crystalline ice-like inclusion


compounds consisting of water molecules hydrogen-bonded to form host cages that
contain small molecules as guest.
The aim of this paper is investigation of possibility to replace methane hydrates by
nitrous oxide (or tetrafluoromethane) hydrates. With this goal there have been
determined the dependencies of composition of the gas hydrate formed from mixtures
of methane and carbon dioxide as well as of formation conditions of these hydrates on
temperature and pressure for different compositions of the gas phase.
For determination of structure and compositions as well as of dynamical and
thermodynamic properties of double hydrates of nitrous oxide or tetrafluoromethane
with methane, the approach developed in our works which is based on a modified
Van der Waals Platteeuw theory of clathrates is used in this paper. In this approach
the crystalline host lattice is considered as non-rigid, able to change volume
depending on the type of the guest molecules and to accomplish first-order phase
transitions. [1]
Phase equilibria in the ternary system hydrategas phaseice (liquid phase) with the
gas mixture of methane and nitrous oxide ( or tetrafluoromethane) are investigated in
dependence on the gas phase composition, pressure and temperature. Equilibrium
compositions of the formed hydrates are determined as a function of the gas phase
composition. It is shown that nitrous oxide content in hydrate exceeds its content in
the gas mixture. Calculations of hydrate formation conditions in the ranges of
temperature 260 300 and pressure 1 100 MPa have been performed. Obtained
results agree, in particular, with the known experimental data for simple hydrates of
methane, nitrous oxide and tetrafluoromethane.
In Russia the work was supported by the Russian Megagrant Project
No 14.B25.31.0030 New energy technologies and energy carriers. Yu.Yu.B. thanks
the RFBR grant No 15-03-01105 for support. The authors also are grateful for the
continuous support of the HITACHI SR16000-M1 supercomputing facility by the
Computer Science Group at the Institute for Materials Research, Tohoku University,
Sendai.
[1] V.R. Belosludov, O.S. Subbotin and D.S. Krupskii et al., Mater. Transactions
48, 704 710 (2007).

Contact: bozhko@niic.nsc.ru

52

Enhanced Hydrogen Storage Performance of Boron-doped


Graphene decorated by Ni-Ti-Mg atoms -A DFT study
Santhanamoorthi Nachimuthu,1 Po-Jung Lai, 1 and Jyh-Chiang Jiang1*
Department of Chemical Engineering, National Taiwan University of Science and
Technology, Taipei 106, Taiwan, R.O.C.

Hydrogen is one of the promising alternative energy source for the future generations
due to its applications in the hydrogen fuel-cell powered vehicles. [1] However, designing
solid state material for hydrogen storage with high gravimetric and volumetric densities near
ambient thermodynamic conditions is one of the challenging tasks. [2], [3] In recent years,
many systems are proposed to store the hydrogen, but, none of them is achieved the US
Department of Energy (DOE) target for 2015. Therefore, it is essential to explore new
materials with desired properties for efficient and economic ways of storing hydrogen. In this
study, we proposed new solid state material for hydrogen storage, which consist of a
combination of both transition and alkaline earth metal atoms decorated boron doped
graphene surface. Hydrogen adsorption and desorption on this material was investigated
using density functional theory calculations. We find that the diffusion barriers for H atom
migration and desorption energies are comparatively lower than the previously designed
mediums and the proposed medium can reach the gravimetric capacity of ~ 6.5 wt %
hydrogen, which is much higher than the DOE target for the year 2015. The proposed
medium will be a good candidate for the efficient Hydrogen storage in practical applications.
Keywords: Hydrogen Storage, Adsorption, DFT, Boron doped graphene, Spillover,
Diffusion barrier.
References:
[1] L. Schlapbach and A. Zuttel, Nature 414, 353 (2001).
[2] K. Mazloomi and C. Gomes, Renew. Sust. Energ. Rev. 16, 3024 (2012).
[3] N. Santhanamoorthi, P.J. Lai, and J.C. Jiang Carbon 73, 132 (2014)

Corresponding author E-mail address: jcjiang@mail.ntust.edu.tw

53

A Novel Acidity Scale for Acidic Catalysts Based on 31P


NMR Chemical Shifts of Phosphine Oxide Probe Molecules
Shing-Jong Huang,1 Anmin Zheng,2 Feng Deng,2 and Shang-Bin Liu3,4
1

Instrumentation Center, National Taiwan University, Taipei, Taiwan


Wuhan Center for Magnetic Resonance, Wuhan Institute of Physics and Mathematics,
Chinese Academy of Sciences, Wuhan, China

Institute of Atomic and Molecular Sciences, Academia Sinica, Taipei, Taiwan


Department of Chemistry, National Taiwan Normal University, Taipei, Country

The acidic strength of liquid acids is normally characterized by the conventional acidbase titration method under aqueous solution, leading to a scaled pK a value. On the
other hand, that of solid acids is commonly classified by titration method using
various amine indicators, and quantified by the Hammett acidity function (H o ). Over
the past few decades, alternative methods have been adopted for acidity
characterization of acid catalysts using calorimetric and thermal measurements, FTIR, and NMR spectroscopy with and without the presence of an adsorbed base
molecules [1]. Herein, a novel technique, which employs 31P NMR using
trialkylphosphine oxides (R 3 PO) as probe molecules, is proposed. Accordingly.
detailed acid features, viz., type (Brnsted vs Lewis), distribution (location and
concentration), and strength of various acid sites can be simultaneously obtained [1].
In addition, results obtained from theoretical DFT calculations [2,3] further verified
that a linear correlation between the observed 31P NMR chemical shifts (CSs) of the
adsorbed base R 3 PO molecules with proton affinity (i.e., acidic strength) may readily
be inferred, which facilitated the 31P-R 3 PO NMR approach for probing not only solid
acids (e.g., microporous zeolites, mesoporous aluminosilicates, mixed metal oxides,
and heteropoly superacids etc.) [4,5] but also liquid acid systems. This approach,
which is capable of covering a wide range of acidic strength (from weak, medium,
strong, to superacid) for both solid and liquid catalysts represents a unique, highly
sensitive acidity characterization technique with excellent CS resolution surpassing
that of common acidity scales (viz., pH, pK a , and H o ) obtained from conventional
titration or non-specific color indicator methods.
[1] Q. Zhao, W. H. Chen, S. J. Huang, Y. C. Wu, H. K. Lee, and S. B. Liu, J. Phys.
Chem. B 106, 44624469 (2002).

[2] A. Zheng, H. Zhang, X. Lu, S. B. Liu, and F. Deng, J. Phys. Chem. B 112,
44964505 (2008).
[3] A. Zheng, S. J. Huang, W. H. Chen, P. H. Wu, H. Zhang, H. K. Lee, L. C. de
Mnorval, F. Deng, and S. B. Liu, J. Phys. Chem. A 112, 73497356 (2008).
[4] A. Zheng, S. J. Huang, S. B. Liu, and F. Deng, Phys. Chem. Chem. Phys. 13,
1488914901 (2011).
[5] A. Zheng, F. Deng, and S. B. Liu, Annu. Rep. NMR Spectrosc. 81, 47108
(2014).
Contact: sbliu@sinica.edu.tw

54

Non-conventional supports for single-atom nanocatalysts for


the oxygen reduction reaction
Aloysius Soon1,2
1

Global E3 Institute and Department of Materials Science and Engineering,


Yonsei University, Seoul, South Korea
2
School of Physics, University of Sydney, NSW, Australia

Platinum-based heterogeneous catalysts are known to play a key role in the fuel cell
technology, such as their use in the low-temperature proton exchange membrane
(PEM) fuel cells. However, the high cost and low lifecycle of these PEM fuel cells
are the major hindrances to its large-scale commercial production [1].
To reduce the high-cost and to optimize its catalytic activity, it was recently proposed
that catalysts with single-Pt atom dispersions and a more durable, corrosion-resistant
TiN support could play an important role in the next generation of Pt-based PEM fuel
cells. In this work, density-functional theory (DFT) calculations were performed to
investigate the adsorption properties of Pt atoms on pristine TiN(001). Optimized
atomic geometries, energetics, and analysis of the electronic structure of the Pt/TiN
system are reported for various surface coverages of Pt anchored at the N surface
vacancy for its catalytic function [2].
In addition, the adsorption of several molecular species (e.g. CO 2 , CO, OH etc.) on
the Pt/TiN(001) surface was explored and for the co-adsorption of CO and OH, it is
found that OH weakens the strong binding of CO and this weakening effect is
enhanced as a function of increasing surface OH coverage, thus affording a possible
design route to mitigate CO poisoning on these Pt-based electrocatalysts for PEM fuel
cell applications [3].
To assess the possible oxygen reduction reaction pathway on these single-atom
nanocatalyst systems, the elementary reaction steps of the oxygen reduction reaction
are investigated on the single Pt atom embedded on the surfaces of TiN(100) and
TiC(100) within the computational hydrogen model (CHE) [4].

[1] Y.-J. Wang, D. P. Wilkinson, and J. Zhang, Chem. Rev. 111, 7625 (2011).
[2] R. Q. Zhang, T.-H. Lee, B.-D. Yu, C. Stampfl, and A. Soon, Phys. Chem.
Chem. Phys. 14, 16552 (2012).
[3] R. Q. Zhang, C.-E. Kim, B.-D. Yu, C. Stampfl, and A. Soon, Phys. Chem.
Chem. Phys. 15, 19450 (2013).
[4] J. K. Nrskov, J. Rossmeisl, A. Logadottir, L. Lindqvist, J. R. Kitchin, T.
Bligaard, and H. Jnsson, J. Phys. Chem. B 108, 17886 (2004).
Contact: Aloysius Soon (aloysius.soon@yonsei.ac.kr)

55

Metal-oxide interface for sustainable hydrogen production


with ethanol steam reforming over Cu-NiO catalyst
Shawn D. Lin*, Li-Chung Chen, Hongkui Cheng, and Chih-Wei Chiang
Department of Chemical Engineering, National Taiwan University of Science and
Technology, Taipei, Taiwan

Hydrogen production through the use of renewable raw materials and renewable
energy is crucial for advancing its applications as an energy carrier. Consequently,
ethanol steam reforming (ESR) that can be carried out with high hydrogen yield at
temperatures below 300 oC is a viable approach. In this study, we fabricated a solid
oxide solution of Cu and Ni within a confined pore space, followed by a partial
reduction, to produce a highly efficient catalyst for ESR. At 300 oC, when ethanol is
completely converted, a H 2 yield of approximately 5 is achieved with CO 2 as the
main carbon-containing product [1]. Table 1 shows comparison of results of recent
low-temperature ESR studies. This demonstrates that H 2 production from bioethanol
is an efficient and sustainable approach. Such a highly efficient ESR catalyst is
attributed to the metal-oxide interface being able to facilitate the transformation of
CH x adspecies from acetaldehyde decomposition into methoxy-like adspecies that
can be reformed easily to produce H 2 , and consequently reduce CH 4 formation.

Table 1. Comparison of low-temperature ESR over different catalysts.


T ( C)

S/E

GHSV(h )

X EtOH (%)

Y H2

S CO2/CH4

Ref.

PtNi/CeO 2

340

750

~100

1.2

~1

43

Pt/CeO 2

300

75

~100

~2

~0.8

41

RhCo/CeO 2

300

10

~300

~100

4.3

1.8

44

RhNi/CeO 2

350

4400

~50

1.2

~0.5

45

Co-hydrotalcite

400

74

66

1.2

13

46

Ni/La 2 O 3

300

~4500

~95

~2

~0.5

47

CuNi/K-Al 2 O 3

300

2.5

--

95

1.3

nil

40

(10Cu-NiO) SC

300

~180

~100

~5

~13

This study

Catalyst

-1

S/E: steam to EtOH molar ratio; GHSV: gas hourly space velocity based on EtOH feed rate;
X EtOH : EtOH conversion; Y H2 : mole of hydrogen formed per mole of EtOH reacted; S CO2/CH4 : mole
of CO 2 formed per mole of CH 4 formed.

[1] L.-C. Chen, H. Cheng, C.-W. Chiang, and S.D. Lin, ChemSusChem (2015) DOI:
10.1002/cssc.201403433.
Contact: sdlin@mail.ntust.edu.tw

56

CO Oxidation and C 2 H 4 Epoxidation Catalyzed by a


Gold Nanoparticle: : A Computational Study
Chen-Chi Lee, Chen-Wei Chan, and Hsin-Tsung Chen*
Department of Chemistry, Chung Yuan Christian University, Chungli District, Taoyuan
City 32023, Taiwan

We have illustrated the detailed mechanism of CO oxidation and C 2 H 4 epoxidation catalyzed


by gold nanoparticles through spin-polarized density functional theory (DFT) calculations.
Calculations on selected model show that the low-coordinated Au atoms of the Au 29
nanoparticle carry slightly negative charges, which enhance the O 2 binding energy compared
to the corresponding bulk surfaces. For CO oxidation, two reaction pathways of the CO
oxidation are considered: the EleyRideal (ER) and LangmuirHinshelwood (LH). For C 2 H 4
epoxidation, a promising trimolecular Langmuir-Hinshelwood mechanism via coadsorbed
ethylene- and CO-assisted reaction is addressed which provides significant insights into the
fundamental catalytic mechanism for ethylene oxidation on small Au nanoclusters. To gain
insights into high catalytic activity of the gold nanoparticles, the interaction nature between
adsorbate and nanoparticle is also analyzed by electronic analysis.

Self- promoted trimolecular mechanism


Versus
Bimolecular mechanism

CO- promoted trimolecular mechanism

[1] Chen, H.-T.; Chang, J.-G.; Ju, S.-P.; Chen, H.-L. Journal of Computational Chemistry. 31,
258-265 (2010)
[2] Chen, H.-T.; Chang, J.-G.; Ju, S.-P.; Chen, H.-L. Journal of Physical Chemistry Letters.
31, 739-742 (2010)
[3] Chen, H.-T.; Chan, C.-W. Physical Chemistry Chemical Physics. Submitted.(2015)

Contact: htchen@cycu.edu.tw

57

Phase Stability of Dichalcogenide Monolayers


Qiang Sun1,2
1

Colleage of Engineering, Peking University, Bejing 100871, China


2
CAPT,Peking University, Bejing 100871, China

As an inorganic cousin of graphene, dichalcogenide monolayers have attracted


considerable attention, which can be extracted from the bulk using mechanical or
solvent based exfoliation method. The former method always leads to a 2D trigonal
prismatic phase (labeled as H-phase), while the solvent based exfoliation method
results in different octahedral coordinated phases. The dependence of the structure on
experimental synthesis method has puzzled scientists for a long time. Using firstprinciple calculations combined with Boltzmann transport equation we have
extensively studied the geometry, energetics, electronic structure, optical absorption
and carrier mobility of various phases. In this talk, we would sumarize our research
on these systems including MoS 2 , MoTe 2 , and VS 2 .

[1] M. Kan, et al., J. Phys. Chem. C 118, 1515 (2014)


[2] M. Kan, et al., Nano Research, DOI 10.1007/s12274-014-0626-5
[3] M. Kan, et al. PCCP (2015, in press)

Contact: sunqiang@pku.edu.cn

58

Quantum Spin Hall Effect in 2D Transition Metal


Dichalcogenide Haeckelites
Hongming Weng,1,2
1

Institute of Physics, Chinese Academy of Sciences, Beijing, China


2

Collaborative Innovation Center of Quantum Matter, Beijing, China

By using first-principles calculations, we have found that a family of two-dimensional


(2D) transition metal dichalcogenide (TMD) haeckelites with square-octagonal lattice
MX2-4-8 (M = Mo, W and X = S, Se and Te) can host quantum spin Hall (QSH)
effect. The phonon spectra indicate that they are dynamically stable and the largest
band gap is predicted to be around 54 meV, high- er than room temperature. These
will pave the way to potential applications of topological insu- lators (TIs). We have
also established a simple tight-binding (TB) model on a square-like lattice to achieve
topological nontrivial quantum states, which extends the study from honeycomb
lattice to square-like lattice and broads the potential topo- logical material system
greatly.

[1] S. M. Nie, Zhida Song, Hongming Weng, and Zhong Fang, arXiv: 1503.09040

Contact: hmweng@iphy.ac.cn

59

Improving Performance of Electronic and Thermoelectric


Graphene Devices by Strain Engineering
Huy-Viet Nguyen,1 V. Hung Nguyen,1,2 M. Chung Nguyen,2 J. Saint-Martin,2 and
P. Dollfus2
1

Center for Computational Physics, Institute of Physics, Vietnam Academy of


Science and Technology, Hanoi, Vietnam
2
Institut d'Electronique Fondamentale, UMR8622, CNRS, Universit Paris Sud,
91405 Orsay, France

Graphene, a two-dimensional (2D) mono-layer material, is expected to become one of


the next generation electronic materials because of its outstanding properties such as
high electron mobility and high thermal conductivity. However, practical applications
of graphene in electronic and thermoelectric devices are hindered due to the lack of
an energy bandgap. So far, many attempts at bandgap engineering in graphene have
been made to overcome these limitations, but each technique still has its own issues.
In this talk, I will present the results of our recent studies which demonstrate that
strain engineering is indeed a promising approach to solve the problem. The presented
results include the improved performance of graphene transistors by using strainedunstrained graphene hetero-channels [1], high thermoelectric figure of merit, ZT, in
vertical graphene juntions [2], and significant improvement of Seebeck coefficient in
vertical devices made of misoriented graphene layers [3].

[1] V. Hung Nguyen, Huy-Viet Nguyen, and P. Dollfus, Nanotechnology 25,


165201 (2014).
[2] V. Hung Nguyen, M. Chung Nguyen, Huy-Viet Nguyen, J. Saint-Martin and P.
Dollfus, Appl. Phys. Lett. 105, 133105 (2014).
[3] V. Hung Nguyen, Huy-Viet Nguyen, J. Saint-Martin, and P. Dollfus,
Nanotechnology 26, 115201 (2015)

Contact: nhviet@iop.vast.ac.vn

60

Dimensionality Effects on Bound Excitons in Few-layer BN


Hung-Chung Hsueh,1and Ching-Ming Wei2
1

Department of Physics, Tamkang University, Tamsui, New Taipei City,


Taiwan Institute of Atomic and Molecular Sciences, Academia Sinica, City, Country
2

Due to reduced charge screening and enhanced electron-electron correlation in lowdimensional systems, significant excitonic effects were observed in the optical
response of atomically thin materials, such as graphene and transition metal
dichalcogenides (MoS 2 , WS 2 ,etc.). This pronounced electron-hole interaction
dominating the optical spectra by inducing strongly bound excitonic states below the
quasiparticle bandgap paves the way for the promising applications of 2D
nanosystems in next-generation optoelectronic and photonic devices. As a graphene
analogue, atomically thin hexagonal BN (h-BN) has recently attracted growing
attention due to its wide bandgap and excellent thermal and chemical stability.
Indeed, large-area mono- and few-layer h-BN have been synthesized successfully
thanks to the progress of modern nanotechnology. To elucidate the dimensional
reduction effects on the spectra of few-layer h-BN nanosheets, in this study, we
perform first-principles GW+BSE calculations which could address properly the
sophisticated quasiparticle self-energy and electron-hole interaction within manyelectron systems. Our results reveal the 1st bright exciton with a huge binding energy
larger than 1.7 eV in monolayer h-BN. Moreover, the excitonic energy of the 1st
bright exciton converges quickly toward 5.45 eV with increasing the layer thickness.
Also, the localization and 2D character of excitons in few-layer h-BN are identified
by analyzing the corresponding real-space exciton wavefunctions.

Contact: hchsueh@mail.tku.edu.tw

61

Nano-defect clusters in irradiated materials:


First-principles assessment and multi-scale modelling
D. Nguyen-Manh, D. Mason, J. Wrobel and S. Dudarev
1

Culham Centre for Fusion Energy, United Kingdom Atomic Energy Authority,
Abingdon, OX14 3DB, United Kingdom

Tungsten and iron based alloys are the main candidates for structural and plasma
facing materials in future nuclear fusion plants [1,2]. Understanding of irradiationinduced vacancy-nanocluster defects behaviour in W&W alloys is one of outstanding
and debate issues since the 1960s although numerous studies have been taken with
regard to the generation and formation of defect structures formed under irradiation.
In this talk, by employing multi-scale approach based on first-principles assessment
for which the inhomogeneous and low electron density in vacancy-cluster regions has
been taken into account, we have performed a systematic study of energetic and
kinetic properties of nano-vacancy clusters in bcc transition metals with a particular
focus on tungsten and origin of the observed anomalous effects of solute segregation
in W alloys. The formation and migration energies of vacancy clusters in nanometersize scale as well as different dissociation pathway of vacancy clusters have been
investigated in order to assess the stability and transformation of different defect
configurations by using density functional theory (DFT) calculations in combination
with molecular relaxation and kinetic Monte-Carlo simulations at various ranges of
temperature and time. Importantly, our ab-initio data base for vacancy cluster
calculations have been used to designing a new interatomic potentials for which the
surface corrections to the embedding functional have been implemented. By crosschecking both formation and migration energies for nanoclusters of vacancies, the
agreement between newly corrected potentials with DFT calculations is very
satisfactory. The predicted temperature of vacancy-cluster dissociation is consistent
not only with observation of the voids but also with the variation of dislocation length
in high-temperature annealing of self-ion irradiated tungsten. Finally, we describe
briefly the extension of a combined DFT cluster expansion formalism [3] by
considering vacancy as a new element in a multi-component alloys in order to study
the origin of coherent precipitates in W-2%Re alloys under irradiation.
[1] F. Hofmann, D. Nguyen-Manh, M.R Gilbert, C. Beck, J. Eliason, A. Maznev,
W. Liu, D. Armstrong, K. Nelson, S. Dudarev, Acta Mater. 89, 352 (2015).
[2] C. Fu, M. Lavrentiev, E. Soulairol, S. Dudarev, D. Nguyen-Manh, Phys. Rev.
B 91, 094430 (2015).
[3] J. Wrobel, D. Nguyen-Manh, M. Lavrentiev, M. Muzyk, S. Dudarev, Phys.
Rev. B 91, 024108 (2015).
Contact: duc.nguyen@ccfe.ac.uk (D. Nguyen-Manh)

62

Multiscale Simulation Study of Structure and Electronic


Properties of Oxidized Silicon Nanowire
Seungchul Kim,1 Mincheol Shin2, and Kwang-Ryeol Lee1
1

Computational Science Research Center, KIST, Seoul, Korea


Department of Electrical Engineering, KAIST, Daejon, Korea

Understanding and controlling the interface morphology of Si/SiO2 is an essential


issue in optimizing the device performance of Si CMOS devices. Especially, the
roughness of the interface in both atomic and electronic structures has been known to
significantly affect the performance. However, experimental methods to characterize
the interfacial roughness are highly limited at present. In the present work, we applied
reactive molecular dynamics simulation by using reactive force field (ReaxFF)
integrated into LAMMPS simulation code [1]. We will present the reactive MD
simulation results of oxidation behavior of Si and Si-NW [2-3]. We will also present
the interfacial roughness on the tunneling of electrons across the dielectric layers and
the transport behavior of electrons in Si-NW devices [4]. Multiscale simulation
approach of the Si/SiO2 interface structure evolution to study the device performance
will be suggested. Finally, web based nano-device simulation platform will be briefly
introduced.
[1] Adri C.T.Van Duin, Siddarth Dasgupta, Francois Lorant, and William A.Goddard
Journal of Physical Chemistry A, 105, (2001).
[2] Byung-Hyun Kim, Mauludi Ariesto Pamungkas, Mina Park, Gyubong Kim,
Kwang-Ryeol Lee, Yong-Chae Chung, Appl. Phys. Lett. 99, 143115 (2011).
[3] Mauludi Ariesto Pamungkas, Minwoong Joe, Byung-Hyun Kim, Kwang-Ryeol
Lee, J. Appl. Phys. 110, 053513 (2011).
[4] Byung-Hyun Kim, Seung-Cheol Kim, Gyubong Kim, Hyo-Eun Jung, Mincheol
Shin, Yong-Chae Chung and Kwang-Ryeol, to be published (2015).

63

Materials Design on Energy-related Materials by Multiscale


Simulations
Hiroshi Mizuseki1
1

Computational Science Research Center,


Korea Institute of Science and Technology (KIST),
Hwarangno 14-gil 5, Seongbuk-gu, Seoul, 136-791, Republic of Korea
Computational materials science has become more and more important in developing
new materials. To design and investigate a wide range of physical and chemical
properties in novel energy-related materials, our group has developed and implemented
some different program codes, including first-principles molecular dynamics, classical

molecular dynamics, Monte Carlo methods, and model calculations. In this


presentation we will present the simulation results of novel models for energy-related
materials, such as nanoscale materials, photovoltaics materials, and photocatalyst
material. A reliable investigation of reaction process, chemical reactions on titanium
dioxide surface are addressed from first principles using time-evolving timedependent density functional theory. In the present study, we discussed the initial
stage of dissociation reaction on titanium dioxide considering the electron excited
state by TOhoku Mixed Basis Orbitals ab initio program (TOMBO) code [1].
We are grateful for the financial support from the Korea Institute of Science and
Technology (Grant No. 2E24630, Development of multi-scale simulation technique
for hierarchically structured photocatalyst) and Center for Convergent Chemical
Process. This research used computational resources of the HPCI system provided by
Cyberscience Center, Tohoku University, Information Initiative Center, Hokkaido
University, Information Technology Center, Nagoya University, and Academic
Center for Computing and Media Studies, Kyoto University through the HPCI
System Research Project (Project ID: hp140063, hp150018, hp150032).
[1] S. Ono, Y. Noguchi, R. Sahara, Y. Kawazoe, and K. Ohno, Comput. Phys.
Comm. 189, 20 (2015).
Contact: mizuseki@kist.re.kr

64

Study of electronic structures and thermoelectric properties


on conjugated ethylenetetrathiolate metal polymers
T. Seike1, K. Akai1, S. Yamamoto1, H. Anno2, N. Toshima2
1Yamaguchi University, Yamaguchi, Japan
Tokyo University of Science Yamaguchiy, Sanyo-Onoda, Japan

Conjugated conducting polymers are candidate of high performance thermoelectric


materials, because they have some advantage; low lattice thermal conductivity, light
weight, low cost, no-toxic and so on. Many conjugated thermoelectric polymers show
p-type conduction and good thermoelectric performance, for example, PEDOT/PSS
with zT~0.42 (T= 297K) [1]. On the other hand, thermoelectric polymers
characterized by n-type conduction are much less and it is the issue to find good ntype polymers. Recently, it was demonstrated that a metal complex polymer: poly
[Nax(Ni-ethylenetetrathiolate (ETT))] has a good n-type thermoelectric performance
[2]. This polymer poly[Nax(Ni-ETT)] will be intrinsic semiconductor with the Na
concentration x=2. But the amount of x is smaller than 2 in the synthesized polymers.
As a concentrated Na atom supplies an electron in the polymers, the lack of Na atoms
from x=2 brinies hole concentration and p-type carriers. It is a puzzle. To discuss
about this point, that is, the origin of n-type carrier in the polymers, we calculated the
electronic structure of an isolated single chain of poly-[M-ETT](M=Fe, Co, Ni, Cu).
The results are very interesting. In M=Fe and Co, M-ETT is Ferro-magnetic, and in
M=Ni and Cu, M-ETT is non-magnetic. And then except M=Ni each M-ETT is
metallic and only Ni-ETT is semiconducting that is characterized by a band gap with
E g =0.45eV. This work is supported by MEXT Regional Innovation Cluster Program
(Global type) Yamaguchi Green Valley
[1] Kim. et al., Nature. Mat. 12 (2013) 719.
[2] Sun et al., Adv. Mater. 24 (2012) 932.

Contact: akai@yamaguchi-u.ac.jp

65

First-Principles Study on Electric and Dielectric Properties


of Metal-Oxide Heterostructures in Nanoscale Devices
Satoshi WATANABE,1 Bo XIAO,1,* and Shusuke KASAMATSU2
1

Department of Materials Engineering, The University of Tokyo, Tokyo, Japan


* Present affiliation: College of Chemistry and Chemical Engineering,
Yantai University, Yantai, China
2
Institute for Solid State Physics, The University of Tokyo, Kashiwa, Japan

Metal-oxide heterostructures play important roles in various novel electronic devices.


Downsizing of such devices necessitates the microscopic understanding on their
electric and dielectric properties. In getting this understanding, significant
contribution of first-principles simulations is expected. In this presentation, we
discuss this issue, showing our recent results on the following two subjects.
1) TaO x -based resistive switching devices: Oxide-based resistive switching devices
have been investigated actively because of its high potential as next-generation
memory. Amorphous-TaO x based devices are especially promising. [1],[2] To obtain
atomistic understanding on the behaviors of these devices, we examine the structures
and electric properties of the conductive filaments in Cu/TaO x /Pt [3] and Pt/TaO x /Pt
heterostructures. [4] In particular, for the latter with x < 2.5, our results suggest that
the Ta-Ta bonding, not O vacancy chain, mainly contributes to the conduction path.
We also discuss the migration behaviors of metal and oxygen ions in TaO x .
2) Utilization of ferroelectric negative capacitance in MOS-FET: High-k dielectrics
has been introduced into MOS-FET in place of silicon oxide to reduce the size of
capacitors. Unfortunately, metal/high-k interfaces often suffer from degraded
dielectric response, and it is shown that a significant portion of this interface dead
layer effect is intrinsic. [5] Using a first-principles approach named orbital
separation approach, [6] we explore the possibility of canceling the dead layer effect
by sandwiching a few layers of ferroelectric BaTiO 3 between the SrRuO 3 electrode
and SrTiO 3 , owing to the appearance of negative capacitance in BaTiO 3 .
Part of the above works were done in collaboration with Prof. T. Gu, Prof. T. Tada,
Dr. A. Tawara, Prof. C. S. Hwang and Prof. S. Han.
[1] T. Sakamoto, K. Lister, N. Banno, T. Hasegawa, K. Terabe, and M. Aono,
Appl. Phys. Lett. 91, 092110 (2007).
[2] M.J. Lee, C.B. Lee, D. Lee, S.R. Lee, M. Chang, J.H. Hur, Y.B. Kim, C.J.
Kim, D.H. Seo, S. Seo, U.I. Chung, I.K. Yoo, and K. Kim, Nat. Mater. 10, 625
(2011).
[3] B. Xiao, T. Gu, T. Tada, and S. Watanab, J. Appl. Phys. 115, 034503 (2014).
[4] B. Xiao, and S. Watanabe, Nanoscale 6, 10169 (2014).
[5] M. Stengel, and N. Spaldin, Nature 443, 679 (2006).
[6] S. Kasamatsu, S. Watanabe, and S. Han, Phys. Rev. B 84, 085120 (2011).
Contact: watanabe@cello.t.u-tokyo.ac.jp

66

Three-connected Networks of Si in Disilicides


Jian-Tao Wang,1* Changfeng Chen,2 and Yoshiyuki Kawazoe3
1
Institute of Physics, Chinese Academy of Sciences, Beijing 100190, China
2
Department of Physics, University of Nevada, Las Vegas, Nevada 89154, USA
3
New Industry Creation Hatchery Center, Tohoku University, Sendai 980-8579, Japan
Under ambient conditions, BaSi 2 adopt the BaSi 2 -type orthorhombic structure, but SrSi 2 has
the SrSi 2 -type cubic structure. Under high-pressure and high-temperature conditions,
orthorhombic BaSi2 transforms into SrSi 2 -type cubic and EuGe 2 -type trigonal structures, and
the trigonal phase can exist under ambient conditions, showing a metallic and
superconducting behavior. On the other hand, orthorhombic BaGe 2 and SrGe 2 transform into
tetragonal and trigonal structures, respectively. Each phase of disilicides and digermanides is
characterized by a unique three-connected Si or Ge configuration: isolated tetrahedra in the
orthorhombic phase; two-dimensional three-connected (2D3C) corrugated layers in the
trigonal phase; and three-dimensional three-connected (3D3C) nets in both cubic and
tetragonal phases. All of the Si and Ge sublattices satisfy the (8-N) rule, which requires a
formal transfer of valence electrons from the divalent metal atoms to Si or Ge atoms, which
then become isoelectronic with group V elements. One can regard BaSi 2 formally as
Ba2+[Si-] 2 , and accordingly, Si 4 tetrahedra are preferred in the orthorhombic phase, which is
similar to the structural arrangement in white phosphorus. Since the orthorhombic phases
have a high compressibility with a larger volume, the more densely packed cubic, trigonal, or
tetragonal phases can be produced under pressure. As a result, the corrugated layers of Si in
the trigonal phase are similar to the crystal structures adopted by black phosphorus at high
pressures, and the cubic Si nets are congruent to the pressure-induced structure of cubic
gauche nitrogen (cg-N).
We here present ab initio calculations of pressure-induced structural phase transitions of
BaSi 2 , BaGe 2 , and SrGe 2 and show that Si tetrahedra in orthorhombic BaSi 2 tend to convert
to corrugated layers in the trigonal phase under high pressure with bond breaking along the b
axis, and a three-dimensional Si net in the cubic phase is stabilized energetically at low
pressure. The orthorhombic semiconductortotrigonal metal conversion is also preferred for
SrGe 2 both energetically and kinetically. However, Ge tetrahedra in BaGe 2 tend to convert to
a ThSi 2 -type tetragonal net with bond breaking around the c axis. The kinetic barriers are
large for both the reaction (0.43 eV under compression) and the counter-reaction (0.39 eV
under decompression) for BaSi 2 , which explains the stability of the trigonal and cubic phases
at room temperature and the high-temperature requirement for the phase transitions.

Email: wjt@aphy.iphy.ac.cn

Relative publications
[1] Phase stability and transition of BaSi2-type disilicides and digermanides, J. T. Wang, C. F.
Chen, and Y. Kawazoe, Phys. Rev. B 91, 054107 (2015).

67

Phononic Properties of Metal Chalcogenides Bi2S3 and


Sb2S3: A First-Principles Study
Chee Kwan Gan,1 Kun Ting Eddie Chua,2 and Yun Liu1
1

Institute of High Performance Computing, 1 Fusionopolis Way, #16-16 Connexis,


Singapore 138632, Singapore
2
Harvard-Smithsonian Center for Astrophysics, 60 Garden Street, Cambridge,
MA 02138, USA

The lattice vibrational studies of a crystal is important to an understanding of phase


stability, phase transitions, thermodynamics, Raman and infrared spectroscopies. We
present a lattice dynamical study on the orthorhombic bismuth sulphide [1] and
antimony sulphide [2] using the supercell force-constant method. We find that the
slow decay of the interatomic force constants for these compounds critically demand
the use of a large supercell of that consists of 320 atoms. Our results provide a proper
guideline for the use of the popular supercell force-constant method: the supercell
size must be carefully be tested along with other parameters such as the kinetic
energy cutoff, the Brillouin zone sampling or the self-consistent convergence criteria.
The phononic study of Sb2S3 [3] provides a direct evidence of the experimentally
observed coherent phonon dynamics generated via the impulsive stimulated-Raman
scattering mechanism.

[1] Y. Zhao, K.T.E. Chua, C.K. Gan, J. Zhang, B. Peng, Z. Peng, and Q. Xiong,
Phys. Rev. B 84 (2011) 205330.
[2] Y.Liu, K.T.E. Chua, T.C. Sum, and C.K. Gan, PCCP 16 (2014) 345.
[3] W. K. Chong, G. Xing, Y. Liu, E.L. Gui, Q. Zhang, Q. Xiong, N. Mathews,
C.K. Gan, and T.C. Sum, Phys. Rev. B 90 (2014) 035208.

Contact: ganck@ihpc.a-star.edu.sg

68

A Pentagon Based Carbon Sheet


Qian Wang 1,2
1

Center for Applied Physics and Technology, Peking University, Beijing, China

Department of Physics, Virginia Commonwealth University, Richmond, VA,USA

Carbon is an amazing material showing many faces - from graphite and diamond in
bulk to C60 fullerene, nanotube, and graphene at the nanoscale. With the exception of
diamond, pure hexagons or hexagons with combination of pentagons are the basic
building blocks of all known carbon materials. The only form of carbon in cluster
phase that is composed entirely of pentagons is C20 fullerene. No other form of
carbon made exclusively of pentagons is known. Based on density functional theory
and ab initio molecular dynamics, we carried out an extensive study to explore the
possibility of forming a new phase of carbon composed entirely of pentagons. We
demonstrate the existence of an all-pentagon nanosheet, penta-graphene, which is
dynamically, thermally and mechanically stable. Not only penta-graphene has novel
properties but also it can be rolled up to form one-dimensional pentagon-based
nanotube and stacked to form three dimensional (3D) stable structures. The versatility
of penta-graphene and its derivatives are expected to have broad applications in
nanoelectronics and nanomechanics.

Contact: qianwang2@pku.edu.cn

69

Quantum-confinement and Structural Anisotropy result in


Electrically-Tunable Dirac Cone in Few-layer Black
Phosphorous
Importance of interlayer interactions beyond van der
Waals
Kapildeb Dolui1, Xin Luo1,2 and Su Ying Quek1
1

Department of Physics and Centre for Advanced 2D Materials and Graphene


Research Centre, National University of Singapore, Singapore
2
Institute of High Performance Computing, Singapore

2D layered materials are well-known to exhibit interesting phenomena due to


quantum confinement effects. We show that quantum confinement, together with
structural anisotropy in few-layer black phosphorus thin films, results in an electricfield induced formation of a Dirac cone in black phosphorus thin films below a
critical thickness. Using density functional theory calculations, we show that an
electric field applied normal to a 2D black phosphorus thin film can reduce the direct
band gap of few-layer black phosphorus. Further increasing the electric field strength
beyond a critical value can induce a Dirac cone in the system, provided the black
phosphorus film is sufficiently thin. The resulting Fermi velocities are similar in
magnitude to that in graphene. We show that the Dirac cone arises from a highly
anisotropic interaction term between the frontier orbitals that are spatially separated
due to the applied field, on different halves of the 2D slab. When this interaction term
becomes vanishingly small for thicker films, or when the interactions between layers
in black phosphorus are turned off, the Dirac cone can no longer be induced, resulting
instead in a normal metal.[1] We show that there exist sizable covalent interlayer
interactions that are anisotropic in nature in few-layer black phosphorus, which
cannot be considered to be a typical van der Waals layered material. These sizable
interactions also result in a significant change in the frequency of the interlayer
breathing phonon mode as a function of layer thickness, a result that has been
confirmed by Raman spectroscopy experiments.[2]
[1] Kapildeb Dolui and Su Ying Quek, Quantum-confinement and Structural
Anisotropy result in Electrically-Tunable Dirac Cone in Few-layer Black
Phosphorous, submitted.
[2] Xin Luo, Xin Lu, Gavin Kok Wai Koon, Antonio H. Castro Neto, Barbaros
zyilmaz, Qihua Xiong, and Su Ying Quek, Large Frequency Change with
Thickness in Interlayer Breathing Mode - Significant Interlayer Interactions in
Few Layer Black Phosphorus, submitted

Contact: phyqsy@nus.edu.sg

70

Graphene, Graphane, and Their Composites


Chih-Kai Yang,1 Chi-Hsuan Lee,1 and Bi-Ru Wu2
1

Graduate Institute of Applied Physics, National Chengchi University, Taipei,

Taiwan, ROC
Center for General Education, Chang Gung University, Kueishan, Taiwan, ROC

We show by density functional calculations that graphene and graphane, the latter
being the product of complete hydrogenation of the former, can form a variety of
structures and composites that have interesting physical properties. A continuous
chain-like distribution of hydrogen vacancies in graphane will result in conduction of
linear dispersion. The same conduction also occurs for chain-like vacancies in an
otherwise fully fluorine-adsorbed graphene. Graphane with two zigzag H-vacancy
chains segregated by one or more H chain is generally a nonmagnetic conductor or
has a negligible band gap. However, the same structure is turned into a semiconductor
and generates a magnetic moment if either one or both of the vacancy chains are
blocked by isolated H atoms. If H-vacancy chains are continuously distributed, the
structure is similar to a zigzag graphene nanoribbon embedded in graphane. It is also
found that the embedded zigzag graphene nanoribbon is antiferromagnetic, and
isolated H atoms left in the 2-chain nanoribbon can tune the band gap and generate
net magnetic moments. Similar effects are also obtained if bare carbon atoms are
present outside the nanoribbon. These results are useful for designing graphene-based
nanoelectronic circuits. It is also found that the structure consisting of an armchair
single-walled carbon nanotube deposited on a graphene nanoribbon is greatly
strengthened by the further adsorption of titanium or vanadium chain. Band structures
reveal strong hybridization between the 3d orbitals of the transition metals and 2p
orbitals of the carbon atoms. For Ti adsorption at the ribbon center, the chain is
nonmagnetic while the ribbon remains antiferromagnetic. For adsorption at the edge,
however, magnetism totally disappears at the coupling side. Magnetism for V chain
adsorption is even more complicated. The results point to a new way for synthesizing
nanowires and possible application in robust nanoelectronic circuits.

Contact: ckyang@nccu.edu.tw

71

CsSn(X x Y 1-x ) 3 (X and Y = Cl, Br, and I) mixed perovskites


for photovoltaics
Arpan Krishna Deb1 and Vijay Kumar1,2
1
Center for Informatics, School of Natural Sciences, Shiv Nadar University, NH91,
Tehsil Dadri, Gautam Buddha Nagar -201314, Uttar Pradesh, India.
2
Dr. Vijay Kumar Foundation, 1969 Sector 4, Gurgaon 122001, Haryana, India

Abstract
Recent achievements of about 20% efficiency of conversion of solar energy in to
electrical energy using organo-metallic perovskites have created great excitement
about the bright prospects of producing cheaply electrical energy and save
environment. However, the organo-metallic halide CH 3 NH 3 PbI3 has the problem of
stability and improved materials are needed. We have carried out a detailed study [1]
on mixed inorganic perovskites CsSn(X x Y 1-x ) 3 , X and Y = I, Cl, and Br using ab
initio calculations within a plane wave pseudopotential approach. Our results show
that in all these cases there is a direct band gap whose value within GGA can be tuned
to around 1 eV by varying the compositions of X and Y. We shall discuss the atomic
and electronic structure. It is found that the top of the valence band and the bottom of
the conduction band have p character and therefore it is very likely that p to p optical
transitions will occur in these materials and these are highly favorable for
photoabsorption. Our results suggest that these inorganic perovskites have the desired
features similar to the organic perovskites to achieve high efficiency of photoresponse with the advantage of the materials stability. Our results on mixed systems
would also be relevant to the understanding of the mixed organo-metallic perovskites.
This work has been performed on the high performance computing facility Magus of
the Shiv Nadar University.
[1] A. K. Deb and Vijay Kumar, submitted for publication.

72

Exciton Diffusion and Charge Separation in Organic


Photovoltaics
Gang Lu
Department of Physics, California State Univerisity Northridge, California, USA

Exciton diffusion and interfacial charge separation are crucial to the performance of
organic photovoltaics (OPVs). The ability to predict exciton dynamics and understand
charge separation mechanisms from first-principles represents a significant challenge
and opportunities in rational design of OPVs. In this talk, I will summarize our recent
effort to develop computational approaches including a large-scale TDDFT
formulation with range-separated hybrid functionals, non-adiabatic molecular
dynamics and excited-state force calculations, all based on plane-waves and
pseudopotentials. These approaches are then brought to bear on key problems in
OPVs, such as prediction of exciton diffusion length and lifetime in disordered
organic materials, the role of hot excitons in charge separation, and phonon-assisted
exciton dynamics. Finally, I will briefly address the open questions and challenges in
first-principles modeling of OPVs.
The work was supported by the NSF and ONR.

Contact: ganglu@csun.edu

73

Linking Experiment and Theory for 3D Networked


Binary Metal Nanoparticle -Triblock Terpolymer
Superstructures
Kahyun Hur,1
1

Center for Computational Science, Korea Institute of Science and Technology,


Seoul, Korea

Controlling superstructure of binary nanoparticle (NP) mixtures in 3D from selfassembly opens enormous opportunities for the design of novel materials with unique
properties for a variety of applications. Here we present a synthetic approach toward
such materials from bottom-up type block copolymer (BCP)metal nanoparticle (NP)
co-assembly. A BCP was used as a structure-directing agent for controlling spatial
arrangement of metal NPs. Structure control of functional NPs at the nanoscale
provides facile routes to nanostructured materials. The intimate coupling of synthesis,
in-depth electron tomographic characterization, and a recently developed field theory
enables exquisite control of superstructure in highly ordered porous 3D continuous
networks from single and binary mixtures of metal NPs.[1] Results provide design
rules for next generation mesoporous network superstructures from binary NP
mixtures for potential applications in areas including catalysis and plasmonics

[1] Li, Z.; Hur, K.; Sai, H.; Higuchi, T.; Jinnai, H.; Gruner, S. M.; Wiesner, U.
Linking Experiment and Theory for 3D Networked Binary Metal
NanoparticleTriblock Terpolymer Superstructures, Nature Commun. 5,
3247 (2014). Equally contributed

Contact: khur@kist.re.kr

74

Roles of Amine and Iron Oxide on Exfoliation of Graphite


Toyoko Imae1,2
1

Graduate Institute of Applied Science and Technology and 2Department of Chemical


Engineering, National Taiwan University of Science and Technology, Keelung Road,
Section 4, Taipei 10607, Taiwan

Graphene can be prepared from a graphite intercalation compound (GIC)


with acceptor-type intercalator, FeCl 3 . When the FeCl 3 -GIC is treated with
primary amines at 90 C for 6 h, the GIC is expanded to a few layers [1].
The expansion is further facilitated, as the alkyl chain of primary amines
becomes longer, while tertiary amines cannot penetrate inside the GIC
because of their structural steric hindrance. The primary amine adsorbed in
the GIC is oriented to form a bilayer by an indirect reaction among
FeCl 3 -graphene-amine, and this process plays an important role on the
expansion of GIC, as contrasted to the reaction of primary amines with
donor-type GICs. Then the expanded-GIC is sonicated to exfoliate the
graphene sheets. The obtained material indicated a superparamagnetic
property due to the remaining iron compounds. This approach using
FeCl 3 -GIC and primary amine is preferable for the mass production of
graphene because of the mild reaction condition and the short treatment time
for exfoliation from the chemically stable FeCl 3 -GIC. Moreover, the
magnetization of graphene nano-composites could be useful for the
magnetic-recovery process, electromagnetic heating, and the other
applications.

[1] M. Ujihara, M. M. M. Ahmed, T. Imae and Y. Yamauchi, J. Mater. Chem. A, 2, 4244


(2014).
Contact: imae@mail.ntust.edu.tw

75

Electronic structure and Transport properties of Graphene


Nanoribbons
Soubhik Chakrabarty1, A.H.M. Abdul Wasey1, Ranjit Thapa2 and G.P. Das1
1

Department of Materials Science, Indian Association for the Cultivation of


Science, Kolkata-700032, India
2
SRM Research Institute, SRM University, Kattankulathur - 603203, India.

Transition from an unconfined graphene monolayer to a confined graphene


nanoribbon (GNR) with Armchair (AGNR) or Zigzag (ZGNR) edges, results in the
opening of a direct band gap that decreases with increasing ribbon width [1]. While
AGNRs are non magnetic, ZGNRs are magnetic with antiferromagnetic coupling
between the two edges. Their electronic properties are sensitive to several factors viz.
chemical doping, modification of edges, creation of defects, application of electric
field etc. --- thereby making these GNRs potential candidates for device applications.
For example, asymmetric edge passivation of ZGNR may change the magnetic
coupling between the two opposite edge atoms. And Boron or Nitrogen doped
ZGNRs with asymmetric edge hydrogenation exhibit half-metallicity which can be
exploited in spin filter devices [2]. AGNRs can be made p-type / n-type by B / N
doping, and many B-N doped AGNR based nano-electronic rectifiers and negative
differential resistance (NDR) devices have been proposed. On the other hand,
vacancy defect creates electron hole asymmetry in AGNRs. This tuning of
electronic property of AGNR by introduction of defect has led us to propose a AGNR
based device which shows high rectifying efficiency and robust NDR [3].
In this talk, we shall give an overview on this class of GNRs and then discuss the
electronic structure as well as transport properties of divacancy defected AGNRs, that
we have carried out within the framework of density functional theory and
nonequilibrium Greens function formalism.
[1] Young-Woo Son, Marvin L. Cohen, and Steven G. Louie, Phys. Rev. Lett. 97,
216803 (2006)
[2] Jun Kang, Fengmin Wu and Jingbo Li, Appl. Phys. Lett 98, 083109 (2011)
[3] Soubhik Chakrabarty, A.H.M. Abdul Wasey, Ranjit Thapa and G.P.
Das,
cond-mat.mtrl-sci arXiv:1409.5859v1; and currently under review for
publication.

Contact: msgpd@iacs.res.in

76

Atmospheric-pressure controllable synthesis of heteroatomdoped carbon nanomaterials and its applications for
electrochemical energy storage and conversion
Wei-Hung Chiang1, Yan-Sheng Li1, Guan-Lin Chen1, Ta-Jen Li2, Min-Hsin Yeh2,
Lu-Yin Lin3, Yow-An Leu2,4, and KuoChuan Ho2,4
1

Department of Chemical Engineering, National Taiwan University of Science and Technology, Taipei
10607, Taiwan
2
Department of Chemical Engineering, National Taiwan University, Taipei 10617, Taiwan
3
Department of Chemical Engineering and Biotechnology, National Taipei University of Technology,
Taipei, 10607, Taiwan
4
Institute of Polymer Science and Engineering, National Taiwan University, Taipei 10617, Taiwan

Recent theoretical and experimental studies have suggested that heteroatom-doped carbon
nanomaterials including carbon nanotubes (CNTs) and graphenes as novel materials with
exceptional electrochemical property due to the heteroatom doping, making them
particularly attractive from both scientific studies and innovation applications including
every storage and conversion, and electrochemical biosensing. Nevertheless, there are few
reports investigating the effect of the heteroatom dopant concentrations in carbonaceous
materials on their electrochemical properties. The difficulty is because of the lacking of
efficient processes to precisely control the heteroatom dopant concentrations on the carbon
surface.
Here we show that boron-doped CNTs (BCNTs) with tunable boron atomic concentration
ranging from 0.4 to 3.9 atomic percentage (at%) can be synthesized by an atmosphericpressure solution-assisted substituion reaction. Mixtures of pristine CNTs and boron oxide
(boron precursor) were heated at elevated temperatures (900~1200 oC) in argon (Ar)
atmospheres. We found that boron atomic concentrations in the nanotubes could be tuned by
simply controlling the reaction temperature and time on the basis of detailed high-resolution
transmission electron microscopy (HRTEM), electron energy loss spectroscopy (EELS), and
X-ray photoelectron spectroscopy (XPS) characterizations. It is also noteworthy from a
practical point of view that the developed atmospheric-pressure synthesis method is
amenable to industrial-scale production since it avoids the need for a vacuum system.
Electrochemical characterization indicates a significant enhancement of 25% in the
amperometric response for BCNTs with 2.1 at% boron atomic concentration than pristine
CNTs, suggesting its potential as efficient catalysts for electrochemical detection of DA. To
explore the possibility of as-produced BCNTs for energy storage, simple supercapacitors
(SCs) using BCNTs as the active electrodes have been fabricated and tested. The highest
specific capacitance value of 40 F g1 is obtained from the cyclic voltammetry analysis with
a scan rate of 50 mV s-1 for the SC electrode with BCNTs containing 2.1 at% boron dopant
concentrations as its active material, with compared to that for the electrode with pristine
CNTs (8.35 F g-1), owing to the lower sheet resistance, better wettability, faster electron
mobility, and more induced functional groups for the former case. Significantly, we found
BCNTs with enhanced thermal stability can be used on counter electrodes of dye-sensitized
solar cells, causing a comparable light-to-electricity conversion efficiency of 7.91% to that
of the Pt-based cell of 8.03%.

77

Activation and Tuning of Two-dimensional Materials for


Hydrogen Evolution Reaction
Shi-Hsin Lin, and Jer-Lai Kuo
Institute of Atomic and Molecular Sciences, Academia Sinca, Taipei, Taiwan
email: albert.shihsin.lin@gmail.com
We theorectically investigated applications of two-dimensional materials for the
hydrogen evolution reaction (HER). The large surface area to volume ratio and
tunable electronic properteis of two-dimensional materials make them promising for
catalytic applications. Recently, monolayer 1H MoS 2 is found to be a good catalyst
for HER. However, it was found that only edge sites are active, leaving the large
basal plane inert. In this work, we explored the activation and tuning of MoS 2 HER
catalytic performance using first-principles calculations. Our analysis on density of
states sheds light on the adsorption mechanism. Accordingly, we proposed suitable
2D materials for hydrogen evolution reaction. These proposed materials are readily
available and hence are of immediate experimental relevance.

78

Deformation behavior of strained single-layer BN, graphene,


and silicene under pressurized blister test
Sirichok Jungthawan and Sukit Limpijumnong
1

School of Physics and


NANOTEC-SUT Center of Excellence on Advanced Functional Nanomaterials,
Suranaree University of Technology, Nakhon Ratchasima 30000, Thailand
2
Thailand Center of Excellence in Physics (ThEP),
Commission on Higher Education, Bangkok 10400, Thailand

The structural deformation of single-layer boron nitride, graphene, and silicene under
different strain conditions (in the range of -0.2 to 0.2) have been investigated using
first-principles density functional theory. The information of lateral relaxation under
uniaxial stress can be extracted from the strain energy surface. The results provide
key mechanical properties of the membranes such as Poissons ratio, ultimate strength,
and in-plane elastic stiffness. Under pressurized blister test, the deformation behavior
of the membrane is describe by using Henckys solution [1]. This solution provides
the membrane profile and the relationship between the pressure and the blister height
that can directly estimate strain in the membrane and adhesion energy of the
membrane with the substrate for real measurement [2].

[1] H. Hencky, Z. fur Mathematik und Physik 63, 311-317 (1915).


[2] S. Koenig, N. Boddeti, M. Dunn, and J. Bunch, Nat. Nano 6, 543-546 (2011).

Contact: sirichok@sut.ac.th

79

Energy Density Functional Approach to Designing


Functional Materials for Energy Applications
K. Srinivasu, B. Modak, K.R.S. Chandrakumar and Swapan K. Ghosh
Theoretical Chemistry Section, Bhabha Atomic Research Center, Mumbai 400 085, India

Designing molecules and materials with tunable properties and functions has
been an important area of research within the broad scope of computational materials
science. A major challenge arises from the hierarchical nature of the length scales
inherent in all material systems. Depending on the nature of interest and application,
an appropriate length scale is chosen for materials modeling. One of the concepts that
has played a major role in the conceptual as well as computational developments
covering all the length scales of interest is the concept of single-particle density. This
encompasses the electron density in the short (microscopic) length scale, particle
number density in the intermediate (mesoscopic) length scale and property density in
the large (macroscopic) length scale. In spite of the differences in the nature of the
density variables used in different length scales, the corresponding theoretical
frameworks involving energy density functional have been found to possess an
underlying unified structure, covering quantum as well as classical systems.
One of the themes of our research has been computational design of molecules
and materials, at different length scales, for use in energy related issues. In view of
the promise of hydrogen energy, hydrogen generation and storage require special
attention. Development of catalyst for solar energy based photochemical splitting of
water and design of suitable materials for efficient reversible storage of hydrogen are
the two challenging problems that are being addressed today. More specifically, metal
decorated carbon based nanomaterials have been considered to be promising for
hydrogen storage in molecular form [1]. Analogously, band gap engineering of
NaTaO 3 through suitable doping has been considered to have enhanced adsorption of
solar radiation in the visible region [2]. The ultimate objective is to design a suitable
catalyst for water splitting using sunlight. Our humble contribution to density based
modelling at different length scales and application to hydrogen energy related issues
of generation and storage of hydrogen will form the subject matter of the talk.
References
[1]. K. R. S. Chandrakumar, and Swapan K. Ghosh, Nano Lett. 8, 13 (2008); (b) K.
R. S. Chandrakumar, K. Srinivasu and Swapan K. Ghosh, J. Phys. Chem. C112,
15670 (2008); (c) K. Srinivasu, and Swapan K. Ghosh, J. Phys. Chem. C 116, 5951
(2012). J. Phys. Chem. C, 116, 25015 (2012), J. Phys. Chem. C, 116, 25184 (2012).
[2]. (a) B. Modak , K. Srinivasu , and Swapan K. Ghosh, J. Phys. Chem. C, 118,
10711 (2014); Phys. Chem. Chem. Phys., 16, 24527 (2014); (b) K. Srinivasu , B.
Modak and Swapan K. Ghosh, J. Phys. Chem. C, 118, 26479 (2014), (c) B. Modak
and Swapan K. Ghosh, Chem. Phys. Lett. 613, 54 (2014)
Contact: skghosh@barc.gov.in

80

Automatizing Ab initio Calculations for Highthroughput Screening


Kanghoon Yim1, Yong Youn1, Joohee Lee1, Kyuhyun Lee1,
and Seungwu Han1
1

Dept. of Materials Science and Engineering in Seoul National University

In this talk, I will present our recent efforts to identify functional oxides
appropriate for specific application targets, utilizing the automatized highthroughput ab initio screening. First, we try to find candidate dielectric materials
that can be used in next-generation memory (DRAM or FLASH) and logic (CPU)
devices, based on the digital database of energy gap, dielectric constant, and
defect formation energies for a large collection of binary and ternary oxides
available on ICSD.[1] Second, I will discuss on finding the ground-state spin
configuration of the anti-ferromagnetic oxides using the model Hamiltonian and
genetic algorithm. Lastly, we try to identify ideal dopants for ZnO when the
material is used for electronic or energy devices. For this end, we develop a series
of automation codes that can carry out ab initio computation of bulk and defect
properties of oxides efficiently and reliably.

[1] K. Yim et al., NPG Asia Mater., in press (2015)


hansw@snu.ac.kr

81

First-principles study of M defects (M = Bi and Al) in


orthorhombic PbZrO 3
Maneerat Chotsawat1,2, Kanoknan Sarasamak1,2,3, Pitiporn Thanomngam1,2,3, and
Jiraroj T-Thienprasert4
1College of Nanotechnology, King Mongkuts Institute of Technology Ladkrabang, Chalongkrung road, Ladkrabang,
Bangkok, 10520, Thailand
2Thailand Center of Excellence in Physics (ThEP Center), Commission on Higher Education, Bangkok 10400, Thailand
3Nanotec-KMITL Center of Excellence on Nanoelectronic Devices, King Mongkuts Institute of Technology Ladkrabang,
Chalongkrung road, Ladkrabang, Bangkok, 10520, Thailand
4Department of Physics, Faculty of Science, Kasetsart University, Bangkok, Thailand 10900

Lead zirconate PbZrO 3 (PZO) is one of the most important ceramic materials due to
its antiferroelectric property, which can be used in many technological applications.
However, due to the toxicity of Pb, there is an attempt to replace Pb with other nontoxic elements. It has been reported that doping with Bi and Al atoms in
orthorhombic-PZO could stabilize the antiferroelectric property in a wide temperature
range and reduce the lead content in material. In this work, we used first-principles
calculations based on density functional theory to investigate the locations of Bi and
Al defects in orthorhombic-PZO by calculating the defect formation energy. Our
calculated results revealed that Bi atom prefers to substitute on both Pb and Zr atoms
depending on the Fermi-level as well as growth condition, while Al atom is likely to
substitute only on Zr atom. In addition, Bi Pb could form a complex defect with Al Zr
or Bi Zr becoming Bi Pb -Al Zr or Bi Pb -Bi Zr complex defect with quite low binding
energy of ~0.1 eV. These results will be used to investigate the stability of
orthorhombic and rhombohedral PZO when doping with Bi and Al atoms.

Contact: fscicwt@ku.ac.th

82

Study of phonon DOS of Carbon crystals from nested K4


lattice to BC-8 structure
Hagita K,1 Sahara R,2 and Kawazoe Y3
1

Department of Applied Physics, National Defense Academy, Yokosuka, JAPAN


2
National Institute for Material Science, Tsukuba, JAPAN
3
Tohoku University, Sendai, JAPAN

K4 lattice [1] is derived from mathematical consideration as highly isotropic


network of coordination number 3 for cubical crystal. This lattice is identical to SRS
lattice [2] (Space group no. 214) which has also various names such as gyroid, Laves
3 1 graph, and (10,3)-a net due to different backgrounds. Several studies of properties
and stabilities of K4 Carbon crystal are reported [3]. In this paper, nested K4 lattice of
the K4 Carbon crystal is considered. The nested lattice is known as double gyroid
which is observed in phase separated polymer system. Atomic positions of nested K4
crystal are given by 32(e) with x=1/8 of space group no. 230. It is equivalent to
combination of a lattice given by 16(c) with x=1/8 of space group no. 206 and its
shifted lattice with (1/2,1/2,1/2). BC-8 structure is given by x=1/10 instead of x=1/8.
BC-8 like structure is expected as Carbon crystal at high pressures around 1500 GPa.
Thus, we can define continuous sequence of positons from nested K4 to BC-8.
We estimated total energy and phonon DOS by using Quantum Espresso (PWscf)
[4] and its PHonon package [4]. Here, we studied Carbon positions with x={20, 21,
22, 23, 24, 25}/200 under cubical crystal with constant unit length (3.370A) at 1500
GPa. We found that value of x for energy minimum is around 22/200. Structures near
nested K4 crystal have negative phonon frequency as shown Figure 1. It is confirmed
that BC-8 like Carbon crystal is stabler than nested K4 Carbon crystal at 1500 GPa.
Table 1. Energy of nested K4 Carbon to BC-8 Carbon around 1500 GPa
x
Energy (Ry)

1/8=25/200 24/200
-171.280
-171.632

23/200
-171.893

22/200
-171.999

21/200
-171.904

1/10=20/200
-171.551

Figure 1. Phonon DOS of Carbon crystals with x=1/8, 23/200 and 21/200.
[1] T. Sunada, Not. Am. Math.Soc. 55, 208-215 (2008). Correction, Not. Am.
Math. Soc, 55, 343 (2008)
[2] M. O'Keeffe, et. al., Acc. Chem. Res. A 41, 17821789, (2008)
[3] M. Itoh, et. al., Phys. Rev. Lett., 102, 055703, (2009)
[4] P. Giannozzi, et. al., J. Phys.:Condens. Matter 21, 395502 (2009).
Contact: hagita@nda.ac.jp
(HPCI project ID: hp140189)

83

Nitrogen Dopants and Vacancy Defects in Graphene


Nanoflakes: Theoretical Study of Size-Dependent Electronic
Excitation Properties
Chih-Kai Lin1
1

Center for Condensed Matter Sciences, National Taiwan University, Taipei,


Taiwan

In this work, finite-sized model molecules of hexagonal graphene nanoflakes


consisted of up to about 400 carbon atoms and embedding with defects have been
established, and their geometric structures, molecular orbitals and valence-electron
excitation properties calculated by DFT and TD-DFT with B3LYP/6-31G(d) and
other functionals. Defects of nitrogen-atom dopants, vacancies, and combinations of
both have been studied. Excitation energies of all low-lying states of all these defects
are found strongly depending on nanoflake sizes with few exceptions. The reason is
revealed by examining MO configuration changes upon excitation, where in most
cases the electron density does not localize in the defect center but disperses to the
edges of the nanoflake instead (Fig 1).
(a)

(c)

(b)

Fig. 1. Molecular orbital maps of (a) LUMO and (b) HOMO of the NV defect in
hexagonal C 216 graphene nanoflake. (c) Excitation energies of low-lying excited
states show a nanoflake-size-dependent trend.

Contact: chihkailin@ntu.edu.tw

84

Excited-state energy functionals and ionization potential theorem

Manoj K. Harbola

Abstract

Similar to the ground-state density functional theory, there is a need for the
development of exchange-correlation functionals for excited-states within time-independent
individual excited-state DFT (eDFT). Over the past, our group is involved in developing
energy functionals for excited-states within eDFT based on split k-space method [2]. In this
method, the k-space of homogenous electron gas (HEG) is split according to the occupation
of the orbitals to get an LDA-like functional. The modified local spin-density (MLSD)
exchange functional has been shown to lead to accurate transition-energies [3]. Encouraged
by this, we have been subjecting our method of constructing the functional to more and more
severe tests [3]. With this in mind, we present our recent work on testing the method for
satisfaction of the ionization potential (IP) theorem [1].
According to the IP theorem, the highest occupied Kohn-Sham orbital energy ( max )
for a system is equal to the negative of the ionization potential [4,5]. We have tested the
exchange energy functional and the associated potential derived by splitting k-space against
ionization potential theorem in excited-state density-functional theory. We will present our
results [1] and show why the split k-space method is a proper way of constructing functionals
for excited-states.

REFERENCES
1. M. Hemanadhan, et al., Testing an excited-state energy density functional and the associated
potential with the ionization potential theorem, J. Phys. B: At. Mol. Opt. Phys. 47, 115005
(2014).
2. P. Samal and M. K. Harbola, Local-density approximation for the exchange energy
functional in excited-state density functional theory, J. Phys. B: At. Mol. Opt. Phys. 38, 3765
(2005).
3. M. K. Harbola, et al., Energy functionals for excited states, in Concepts and Methods in
Modern Theoretical Chemistry, Vol. 1 : Electronic Structure and Reactivity, Eds. S. K.
Ghosh and P. K. Chattaraj (CRC Press, Florida), pp. 99-118 (2013).
4. . Nagy and H. Adachi, Total energy versus one-electron energy differences in the excitedstate density functional theory, J. Phys. B: At. Mol. Opt. Phys. 33, L585 (2000).
5. Md. Shamim and M. K. Harbola, Study of asymptotic decay of electronic density for excited
states including auto-ionizing states of many-electron systems, Chem. Phys. Lett. 464, 135
(2008).

85

TAO-DFT and Its Applications to Zigzag Graphene


Nanoribbons
Jeng-Da Chai
Department of Physics, National Taiwan University, Taipei, Taiwan

In this talk, I will briefly describe the formulation of our recently proposed thermallyassisted-occupation density functional theory (TAO-DFT) [1], the density functional
approximations to TAO-DFT [2], and the electronic properties of zigzag graphene
nanoribbons (ZGNRs) studied by TAO-DFT [3]. In contrast to Kohn-Sham DFT,
TAO-DFT is a DFT with fractional orbital occupations given by the Fermi-Dirac
distribution (controlled by a fictitious temperature), for the study of large ground-state
systems with strong static correlation effects. Relative to TAO-LDA (i.e., the local
density approximation to TAO-DFT), TAO-GGAs (i.e., the generalized-gradient
approximations to TAO-DFT) are significantly superior for a wide range of
applications, such as thermochemistry, kinetics, and reaction energies. For
noncovalent interactions, TAO-GGAs with empirical dispersion corrections are
shown to yield excellent performance. Due to its computational efficiency for systems
with strong static correlation effects, TAO-LDA is applied to study the electronic
properties of hydrogen-terminated ZGNRs with different widths and lengths, which is
very challenging for conventional electronic structure methods. Some interesting
results will be presented in this talk.

[1] J.-D. Chai, J. Chem. Phys. 136, 154104 (2012).


[2] J.-D. Chai, J. Chem. Phys. 140, 18A521 (2014).
[3] C.-S. Wu and J.-D. Chai, J. Chem. Theory Comput., DOI: 10.1021/ct500999m,
in press (2015).
Contact: jdchai@phys.ntu.edu.tw

86

First principles study of electronic structures and stability


in structural materials
Ryoji Sahara
National Institute for Materials Science, Tsukuba, Japan

It is important to understand the theories governing the structural and electronic


properties in structural materials in order to effective control of these properties. In
this talk, main results of the following two topics on electronic structure analysis of
structural materials by first-principles calculations are introduced.
First, the electronic structures and structural properties of body-centered cubic (bcc)
titanium alloys were studied. This is because interest in and demand for bcc titanium
alloys are growing due to their high specific strength and good formability(1). To
emulate the random atomic distribution in solid solution state of the alloys, the special
quasirandom structures (SQS) model(2) was adopted. To clarify the phase stability of
bcc Ti-X alloys with respect to the reference hcp phases, the formation energy,
structural parameters, and the electronic properties were analyzed (3-4).
Second, interface strength mechanism by boron in ferritic steels through M 23 (C,B) 6
precipitates was investigated. This is because impurity boron plays an important role
in high chromium heat resistant ferritic steels. It is shown that boron improves the
stability of the precipitates and interface between the precipitates and bcc Fe matrix (5).

References:
(1) P. J. Bania, D. Eylon, R. R. Boyer, and D. A. Koss (ed), Beta Titanium Alloys in
1990s (Warrendale, PA: TMS, 1993) pp 314.
(2) A. Zunger, S-H. Wei, L. G. Ferreira, and J. E. Bernard, Phys. Rev. Lett. 65 (1990)
353.
(3) R. Sahara, S. Emura, S. Ii, S. Ueda, and K. Tsuchiya, Sci. Tech. Adv. Mater. 15
(2014) 035014.
(4) R. Sahara, S. Emura, and K. Tsuchiya, J. Alloys and Compounds 634 (2015) 193.
(5) R. Sahara, T. Matsunaga, H. Hongo, and M. Tabuchi, in submission.
Contact: SAHARA.Ryoji@nims.go.jp

87

Photoelectron Spectroscopy and Theoretical Study of


Platinum Halides PtX n (X = F, Cl, Br, I; n = 2-4)
Miao Miao Wu,1 Gao-Lei Hou,2 Qiang Sun,3 Xue-Bin Wang 2
1 Department of Materials Science and Engineering, China University of Mining
and Technology (Beijing), Beijing 100083, China
2
Physical Sciences Division, Pacific Northwest National Laboratory, P. O. Box
999, MS K8-88, Richland, Washington 99352, USA
3
Department of Materials Science and Engineering and Center for Applied
Physics and Technology, Peking University, Beijing 100871, China

Using density functional theory we have systematically calculated the ground state
geometries, relative stability, electronic structure of the gas-phase platinum halides,
PtXn (X =F, Cl, Br, I; n = 2-4). And PtXn- (X =Cl, Br, I; n = 2-4) anions were also
successfully obtained using electrospray and investigated using photoelectron spectra.
Both the experiments and theoretical calculations showed that PtXn clusters with
n=3,4 are all superhalogens with electron affinities larger than that of chlorine. It is
also found that in these clusters the bonding is dominated by covalent interaction.

Contact: miaomwu@cumtb.edu.cn

88

Ru Catalyzed Hydrodeoxygenation of Aromatic Oxygenates


Derived from Biomass
Cheng-chau Chiu,1
1

Institute of Atomic and Molecular Sciences, Academia Sinica, Taipei, Taiwan

The pyrolysis of woody biomass typically yields a mixture of organic oxygenates


referred as pyrolysis oil. This product mixture need to be upgraded via an
hydrodeoxygenation (HDO) step, to reduce the oxygen content which is associated
with many undesired properties, e.g., low heating values [1].
Experiments addressing the HDO of aromatic species in the pyrolysis oil have used
guaiacol [C 6 H 4 (OH)(OCH 3 )] as a model and showed that, among others, Ru may be
a suitable catalyst for the HDO process [2, 3]. In experiments at around 400 C and
varying H 2 pressures, guaiacol could be transformed to (partially) deoxygenated
aromatic products. While the reaction at ~40 bar H 2 mainly yields benzene [2],
phenol is observed as the main product at reducted H 2 pressures below 1 bar [3].
Computational studies at the DFT-GGA level on the guaiacol HDO over Ru showed
that aromatic C-O bond cleaving steps are rate-determining [4, 5], consistent with the
experimental observation of catechol as an intermediate [2, 3].
Calculations modeling the reactions on terrace sites indicate that removal of the first
O group is kinetically accessible while removal of the second O group is kinetically
hindered. In contrast, both C-O cleavage steps are equally well accessible at step sites
of a Ru catalyst. [4, 5]
Based on the calculated results, an interplay between the different sites on the Ru
catalyst, the H 2 and the adsorbates on the catalyst is proposed. This interaction may
provide a rationalization for the pressure dependence of the product selectivity
observed in experiment.

[1] G.W. Huber, S. Iborra, A. Corma, Chem. Rev. 106, 4044 (2006).
[2] J. Chang, T. Danuthai, S. Dewiyanti, C. Wang, A. Borgna, ChemCatChem 5,
3041 (2013).
[3] S. Boonyasuwat, T. Omotoso, D.E. Resasco, S.P. Crossley, Catal. Lett. 143,
783 (2013)
[4] C.-c. Chiu, A. Genest, A. Borgna, N. Rsch, ACS Catal. 4, 4178 (2014)
[5] C.-c. Chiu, A. Genest, A. Borgna, N. Rsch, Phys. Chem. Chem. Phys.
accepted, DOI: 10.1039/c5cp01027f.

Contact: cheng.chiu@mytum.de

89

Theory for Electronic Couplings and Dynamics of Singlet


Fission in Oligoacene Dimers
Yuan-Chung Cheng, Wei-Chi Chen, Shi-Kai Lin, Jing Sun
Department of Chemistry, National Taiwan University, Taipei City, Taiwan

Singlet exciton fission in organic materials has attracted intensive research attention
recently because of its potential to significantly improve efficiency of solar cells. In
this work, we propose to utilize an intermediate block-diagonalization procedure in
the configuration interaction theory to construct an approximate electronic diabatic
basis to unambiguously interpret the characters of the excited states involved in the
singlet fission of a molecular dimer system. By applying the restricted active space
configuration interaction single and double approach, we show the importance of
considering multi-configuration effects in oligoacene dimers, especially the key role
of double-excitation configurations. Our results allow us to construct effective
electronic model Hamiltonian for siglet fission in oligoacene dimers that exhibits
strong superexchange effective coupling and the near degeneracy condition to explain
the ultrafast SF mechanism. We also demonstrate that a crucial factor is the energetic
position of the charge transferred diabatic state, which remarkably controls the
amplitude of the effective coupling. Therefore, in addition to the near degeneracy of
the lowest lying singlet exciton and the double-triplet state, we conclude that the
lowering of the charge transferred diabatic state energy should also be considered as a
key factor for the design of high efficiency singlet-fission materials. Furthermore, to
investigate the dynamics of singlet fission in model oligoacene dimer systems, we
propose a simple scheme to calculate electron-vibration coupling constants for model
oligoacene systems, enabling us to carry out full quantum dynamics simulations of
the process of singlet fission in polyacene dimers. Our results demonstrate that a selfconsistent theoretical framework based on ab initio quantum chemistry calculations
can be constructed to effectively simulate singlet fission in molecular dimer systems.
Contact: yuanchung@ntu.edu.tw

90

Factors Governing Strong Spin-Orbit Coupling and Fast


Intersystem Crossing in Luminescent Materials: A
Theoretical Perspective
Elise Yu-Tzu Li
1

Department of Chemistry, National Taiwan Normal University, Taipei, Taiwan

Due to the large spin-orbit coupling (SOC) effect in TM complexes, which gives rise
to fast intersystem crossing (ISC) and therefore strong phosphorescence,
organometallic transition metal (TM) complexes hold enormous promise as the active
components in optoelectronic devices. Recently, the design and characterization of
thermally activated delayed fluorescence (TADF) phenomenon in pure organic
systems for optoelectronic applications represents another rising area of rescarch in
organoelectronics. For both class of systems, a thorough understanding in the
fundamentals of photophysical properties from the theoretical perspective is essential
to make major breakthroughs for future extensions. In this talk, I will present our
theoretical assessments on the ISC rate via evaluating SOC strength of major ISC
channels for certain representative TM complexes and twisted donor-acceptor type
heterocyclic organic systems. We focus on qualitative as well as quantitative analyses
of charge transfer (CT)/* contributions to SOC integrals. A careful comparison
between theoretical predictions and experimental behaviours are performed. Through
a close examination of the electronic structure character of these TM complexes, we
sum up a set of empirical rules for organometallic analogous to the El-Sayeds rule
for organic systems. The plausibility of the recently propossed hot-exciton
mechanism in highly efficient luminescent TADF materials will also be discussed.

[1] E. Y. Li, T.-Y. Jiang, Y. Chi, and P.-T. Chou, Phys. Chem. Chem. Phys. 16, 26184
(2014)

Contact: eliseytli@ntnu.edu.tw

91

Tug of war between H 3 O+ versus Ar/OH


Kaito Takahashi,1 Masato Morita, 1 Jheng-Wei Li,1 and Jer-Lai Kuo1
1

Institute of Atomic and Molecular Sciences, Academia Sinica, Taipei, Taiwan

The hydration state of proton and hydroxide in water have attracted attention due
to its fundamental relevance in understanding aqueous chemistry and biology. The
strong ionic hydrogen bond (IHB) between the ion and local water molecules causes
distortions in the hydrogen bonding network compared to pure water. Experimentally,
vibrational spectra of size selected hydrated ionic clusters have been actively utilized
to elucidate the solvation structure. Since one is interested in the local hydration
structure it is important to elucidate the vibrational signature of the H+ motion, or the
OH bonds of the first solvation shell water molecules that directly bound to the OH-.
However due to the strong IHB in these systems, the obtained spectra are very
anharmonic and the usual recipe of using scaled harmonic frequencies or its
perturbative corrections, available in many quantum chemistry packages, breaks
down. In our study we performed accurate vibrational study on the IHB OH
stretching vibrational spectra to elucidate the curious vibrational features observed in
the OH-(H 2 O) 2-4 and H+(H 2 O)Ar 0-3 systems.
In the solvated hydroxide system, we first show that considering local anharmonic
IHB OH stretching vibration as the active vibrations is not enough to account for the
correct peak positions seen in OH-(H 2 O) 3 .[1] Here the anharmonic couplings
between the IHB OH stretching modes are required for the correct peak positions.
Then we will show that for OH-(H 2 O) 2 this coupled IHB OH picture gives peak
positions that are 300 cm-1 blue shifted from the experimental observed spectra. To
remedy this discrepancy, we show that we have to account for the 1:1 resonance
between the IHB OH stretching and the IHB bending vibration. Furthermore, low
frequency vibrations can greatly alter the spectra and for the correct description of the
observed spectra the van der Waals stretching vibration between OH- and solvating
H 2 O molecule have to be considered. However, in this storngly coupled system, the
observed spectra is very broad and making assignements is very arbitrary.
In the Argon solvated proton system, the sharper peaks allows for a stringent test
to validify the accuracy of the caculation. In this system, we have to consider all the
stretching and bending vibration along with the internal rotation of the hydronium ion.
All these vibrations are required to assign the detailed subtle features seen in the
experimental spectra in the region of 1500 to 3800 cm-1.
[1] M. Morita, and K. Takahashi, Physical Chemistry Chemical Physics 15, 114124 (2013).
[2] M. Morita, and K. Takahashi,Physical Chemistry Chemical Physics, 15,
14973-14985.
Contact: kt@gate.sinica.edu.tw

92

Charge Compensation Phenomena


at Ferroelectric Interfaces
Chew K.-H
Center for Theoretical Physics, Department of Physics, University of Malaya,
50603 Kuala Lumpur, Malaysia

In ferroelectric thin film, it is well-known that the polarization discontinuity at surface


induces depolarization field. The depolarization field can be partially or fully
compensated by the migration of free charge within the film or by the free charge in
the environment [1]. Ferroelectric superlattices are currently a topic of active research
because of their striking new behaviours [2]. Superlattices are ideal model systems for
investigating the interface physics of ferroelectrics. In this work, the charge
compensation phenomena at the interfaces in ferroelectric superlattices is investigated
within the framework of the Landau-Ginzburg theory [3]. Interface mixing leads to
polarization continuity or discontinuity in superlattice. Free charge with equal but of
opposite sign for alternate interface builds up to compensate the depolarization effect
in superlattices. We found two possible charge compensation mechanisms by which
the screening charge may build up at interface, depending on the arrangement of
screening charge at interfaces. The screening charge may build up at interface to
induce an internal field that acts against the depolarization effect in the constituent
layer. Another compensation phenomenon is that the built-up charges suppress the
inhomogeneous polarization near at interface, forming a superlattice with a uniform
polarization across the constituent layer.

[1] M. E. Lines, and A. M. Glass, Principles and applications of ferroelectrics and


related materials (Clarendon Press, Oxford, 1977).
[2] J. F. Scott, ISRN Materials Science, 2013, 187313 (2013).
[3] K.-G. Lim, K.-H. Chew, D. Y. Wang, L.-H. Ong, and M. Iwata EPL
(Europhysics Letters) 108, 67011 (2014)

Contact: khchew@um.edu.my

93

Designing Nano-Valves for the Storage of Hydrogen under


High Pressure
Zhi-Feng Liu
Department of Chemistry, the Chinese University of Hong Kong
Hong Kong, China
and
Shenzhen Rsearch Institute, The Chinese University of Hong Kong
Shenzhen, China

Molecular hydrogen is highly compressible, due to its weak van der Waals potential.
With the robust graphene wall, a carbon nanotube could stand up to pressure of 40
GPa. Carbon nanotubes are therefore ideal containers to store hydrogen in high
pressure, but the challenge is to design a nano-valve that could be open and closed in
a non-destructive way. I shall present the designs made in our group, as well as
simulation results on such nano-valves.1-4

References:
1.
H. Y. Chen, D. Y. Sun, X. G. Gong and Z.-F. Liu, Angewandte Chemie-International
Edition 52 (7), 1973-1976 (2013).
2.
D. Y. Sun, H. Y. Chen, J. W. Liu, X. G. Gong and Z.-F. Liu, Phys. Rev. B 79 (3),
0033403 (2009).
3.
D. Y. Sun, J. W. Liu, X. G. Gong and Z.-F. Liu, Phys. Rev. B 75 (7), 075424 (2007).
4.
X. Ye, X. Gu, X. G. Gong, T. K. M. Shing and Z.-F. Liu, Carbon 45 (2), 315-320
(2007).

94

Atomic force microscopy simulation covering wide range


time-scale
Yasuhiro Senda,1 Shuji Shimamura,1 Janne Blomqvist,2 and Risto Nieminen2
1

Department of Applied Science, Yamaguchi University, Yamaguchi, Japan


COMP Centre of Excellence, Department of Applied Physics, Aalto University,
Aalto, Finland

Non-contact Atomic Force Microscopy (AFM) is promising tool capable to


providing atomic resolution images for a variety of materials. As the oscillated
cantilever of the AFM approaches to the surface, its resonance frequency is changed
and it provides an atomic resolution image of the surface. In addition to the change of
resonance frequency, the oscillation of the cantilever is damped and this energy
dissipation also offers a structural atomic image. The origin of energy dissipation,
however, has been the subject of debate over the past decade. We try to show
mechanism of the observed energy dissipation by the computational approach[1,2].
The atomic interaction between the probe and surface has the atomic scale, while the
frequency of the cantilever has the macroscopic time scale (kHz~MHz). The
macroscopic dynamics of the cantilever is perturbed by atomic scale interaction, and
atomic behavior on the surface is also affected by the oscillation of the cantilever. It is
indicated that the dynamical coupling of the cantilever and atoms is closely related
with the observed energy dissipation. Therefore we propose the computational model
connecting the cantilevers oscillation and atomic dynamics. The motion of cantilever
is described by a spring, and the atomic interaction between probe and surface is
calculated by molecular dynamics (MD) method. The motions of the spring and
atoms are concurrently coupled by the MD/continuum hybrid method [3].
We performed a long-time MD calculation and it shows the energy dissipation in
case of sec (MHz) order of cantilevers frequency. The origin of the energy
dissipation will be explained and discussed.

Fig. Schematic view of the present computational model for


AFM. The MD atoms are drawn by circles.

[1] Y.Senda, et al. Integrated Ferroelectrics, 155, 33-38 (2014)


[2] Y. Senda, et al. e-Journal of Surface Science and Nanotechnology, 12, 339 (2014)
[3] G. Kim and Y. Senda, J. of Phys.:Condensed Matter, 19, 246203 (2007)
Contact: Yasuhiro Senda, senda@yamaguchi-u.ac.jp

95

Sparse Modeling for Materials Design


DAM Hieu Chi,1 PHAM Tien Lam,2 and NGUYEN Viet Cuong2
1

Japan Advanced Institute of Science and Technology, Ishikawa, Japan


ESICMM, CMS Institute for Solid State Physics, The University of Tokyo, Japan
2
HPC Systems, Inc., Tokyo, Japan

In the field of materials science, researcher start from synthesizing and characterizing
the physical properties of a series of similar materials. Then, by analyzing the
multivariate correlations between the features describing the synthesized materials
and the corresponding derived physical properties, researchers propose hypotheses for
explaining the nature of the materials and design the materials. In a general term, the
task of materials design is to clarify these correlations and to determine a strategy to
modify the materials to obtain desired properties. However, such multivariate
correlations are usually hidden and difficult to uncover or predict by experiments or
experience.
Motivated by using data mining to promote the materials design process, we develop
several methods to quantitatively model families of materials by sparse modeling,
using their experimental data. The key idea of our methods is to use multiple linear or
nonlinear regressions [1], [2] with regularization technique to solve the sparse
approximation problem on the space of structural and physical properties of materials.
We use cross-validation to consistently and quantitatively evaluate the conditional
relations of each feature on to the target features which we focus on. Analytical
formulas representing relations between the target features and the other features of
materials can also be reconstructed using on the obtained sparse model. The proposed
method can extract from experimental data significant information for the
comprehension of the physics relating to the materials, but also valuable for the
guidance of effective material design.

[1] R. Tibshirani, J. Royal. Statist. Soc B., 58, 267-288 (1996).


[2] CE. Rasmussen, CKI. Williams, MIT Press, (Ed. T Diettrich) (2006).

Contact: dam@jaist.ac.jp

96

Computational Material Discovery using the HPCBased ab initio Methods


Yansun Yao 1,2
1

Department of Physics and Engineering Physics, University of Saskatchewan, 116


Science Place, Saskatoon SK, S7N 5E2, Canada
2
Canadian Light Source, Saskatoon, Saskatchewan, S7N 2V3, Canada

This research project is part of a broad material science program now being
developed jointly by the University of Saskatchewan and the Canadian Light Source.
A main objective is to computationally explore for novel structures and properties of
crystalline solids, and to develop new theoretical methods for synchrotron-based
material science studies. To this end, we are developing a new suite of theoretical
methods for crystalline structural prediction, taking the advantages of high
performance computations, to accurately determine new and practically achievable
geometries of materials formed under diverse physical conditions. Several significant
applications will be shown that highlights the critical guidance our methods can
provide for the synchrotron-based material studies.
Contact: yansun.yao@usask.ca

97

Theoretical study of reaction dynamics for C-X dissociation


of XH 2 C-CCH (ads) /X-CCCH 3(ads) (X= I and Br) adsorbed
on Ag(111) surface
Shao-Yu Lu, Yung Ting Lee and Jyh-Shing Lin*
Department of Chemistry, Tamkang University
Tamsui, Taiwan 25137

Abstract
The reaction dynamics for C-X dissociation within XH 2 C-CCH (ads) (X=Br) and
X-CCCH 3(ads) (X=I) adsorbed on the Ag(111) surface has been investigated by
combining density functional theory (DFT)-based molecular dynamics simulations
with short-time Fourier transform (STFT) analysis of dipole moment autocorrelation
function (DMAF). The initial adsorbed XH 2 C-CCH (ads) will undergo dynamic
fluctuation leading to the final parallel orientation of XH 2 C-CCH (ads) to cause the
C-X scission and then it immediately transforms from propargyl form
(H 2 C-CCH (ads) ) into allenyl form (H 2 C=C=CH (ads )) adsorbed on the Ag(111) surface
at 150K. On the other hand, the initial adsorbed X-CCCH 3(ads) will also undergo
dynamics fluctuation leading to the final parallel orientation of X-CCCH 3(ads) to
cause the C-X scission and it remains as acetylide form (CCCH 3(ads) ) without further
transforming into allenyl form (H 2 C=C=CH (ads) ) adsorbed on the Ag(111) surface at
150K. To further investigate the evolution of different vibrational modes of
XH 2 C-CCH (ads) and X-CCCH 3(ads) along their C-X dissociation pathways, the
STFT analysis is performed to illustrate that 1) the major IR active peaks of
XH 2 C-CCH (ads) such as vCH 2 (2956 cm-1(s) and 3020 cm-1(as)), vCH (3320 cm-1)
and vCC (2150 cm-1) gradually vanish as the rupture of C-X bond occurs and then
the resulting IR active peaks such as C=C=C (1812 cm-1), -CH 2 (780 cm-1) and
-CH (894 cm-1) appear due to the formation of H 2 C=C=CH (ads) which are in a good
agreement with experimental reflection adsorption infrared spectrum (RAIRS) at
temperature of 110K and 200K, respectively, and 2) the major IR active peak of
X-CCCH 3(ads) such as CC (2190 cm-1) will gradually redshift into CC (2038
cm-1) as the rupture of C-X bond occurs due to the formation of CCCH 3(ads) which is
also in a good agreement with the RAIRS at temperature of 110K and 200K,
respectively.

98

Theoretical Study on Task Specific Ionic Liquid for Metal


Extraction from Garbage Caused by Tsunami
Yoshiyuki Kawazoe
New Industry Creation Hatchery Center, Tohoku University, Sendai, Japan, and
Institute of Thermophysics, Siberian Branch, Russian Academy of Sciences, Russia

After 4 years from the big tsunami attaked Tohoku area in Japan, still there
remains a large amount of garbages. They have been collected and moved to limited
areas and classified as stones, steels, woods, etc., and among them there are a large
amount of electronic circuit boards, which contain expensive metals that should be
extracted and reused. We have been trying to extract such metals by using ionic
liquid experimentally and theoretically. The ionic liquid is functionalized by
attaching ligands for extraction of specific metal element, and is called task specific
ionic liquids (TSIL).
Since the properties of TSIL varies strongly as a function of temperature and not
easy to be understood experimentally: especially temperature dependence of viscosity
and hydrophobicity are difficult to be estimated. We have developed a new
theoretical method based on molecular dynamics and hydrodynamics to determine
theoretically the viscosity in TSIL, and successfully applied to compute for several
TSIL.
Among metal extraction studies, up to the present Rh has been the worst to be
extracted efficiently from
garbage in industry. We
studied the properties of
Rh and proposed a new
TSIL,
which
atomic
structure is shown on the
right and is expected to be
suitable for Rh extraction
compared to existing
industrial methods.
In the talk, I will present the recent works on this interesiting new materials, ionic
liquid, for metal extraction from garbage.
The author is thankful to the Tohoku Innovation Materials Technology Initiatives for
Reconstruction for the support of this research. He also is greatful to the HPCI
project for the supply of supercomputer power as the grant ID hp150076, and the
Russian Megagrant Project No.14.B25.31.0030 New energy technologies and energy
carriers .
Contact: kawazoe@imr.edu

99

POSTER PRESENTATIONS

100

Numerically Study of the Aerodynamic Response and


Energy Harvesting of Polyvinylidene Fluoride Piezoelectric
Harvester in a Uniform Flow
Rujun Song, Xiaobiao Shan, and Tao Xie
School of Mechatronics Engineering, Harbin Institute of Technology, Harbin,
China

The energy of air flow is renewable and exists everywhere. It can drive the
piezoelectric energy harvester to vibrate for harvesting energy. Inspired by the
stimulation vibration by air flow and its complicated aerodynamic response, this
paper presents the constructive vibration modes for the energy harvesting of single
piezoelectric flag (SPF) and multi-piezoelectric flags (MPF) in a uniform flow. The
dynamic response and energy harvesting of SPF and MPF are investigated by a 2Dnumerical method. This method is fully coupled fluid-structure-electric (FSE) by
using the immersed boundary-lattice Boltzmann method coupled with Euler-Bernoulli
beam and piezoelectric theory. As an application, the dynamic characteristics of a
single piezoelectric flag at stable state is described, including the flapping amplitude,
frequency, vibration mode, and output voltage. In terms of the MPF, the results show
that in-phase vibration mode as the constructive vibration modes for the energy
harvesting of the MPF can be obtained in one row, one column, three rows and three
columns (33) and five rows and three columns (53) matrix arrangement. The
vibration characteristics of the MPF are influenced by the streamwise and spanwise
gap distances. The drag variations are influenced by the interaction between vortices
shedding from the upstream piezoelectric flag and the surrounding the downstream
flags. Constructive in-phase vibration modes demonstrate that stable voltage output of
each piezoelectric flags can be identified. Multi-times electric energy can be
generated using the MPF compared with the single piezoelectric flag in a uniform
flow.

Contact: songrujunok@126.com

101

A DFT Study on Properites of [BMIM][NTF 2 ] IL


Functionalized with Alkyl Amine Chains
Surya V.J. Yuvaraj1,4, Rodion V. Belosludov2, Vladimir R. Belosludov3,4,6, Ravil
Zhdanov3,4,6, Oleg S. Subbotin3,4,6 , Kiyoshi Kanie4, Kenji Funaki4, Atsushi
Muramatsu4,Takashi Nakamura4, and Yoshiyuki Kawazoe1,5
1

New Industry Creation Hatchery Center, Tohoku University, Japan.


2
Institute for Materials Research, Tohoku University, Japan.
3
Nikolaev Institute of Inorganic Chemistry SB RAS, Novosibirsk, Russia.
4
Institute of Multidisciplinary Research for Advanced Materials, Tohoku University,
Japan.
5
Institute of Thermophysics, SB RAS, Novosibirsk, Russia.

Ionic Liquids possess unique properties that make them applicable in various fields of
chemistry. The non-volatility, stability and tunable solubility of the ILs make them as
suitable solvents for metal extraction instead of traditional volatile organic solvents.
They are also considered as green solvents due to its less toxic nature. Our research
group focuses on rare metal extraction using different task specific ionic liquids
(TSILs). Previously, we have examined the hydrophobic nature of two different
TSILs that are designed for rare metal extraction using DFT [1].
Recently, our experimental group have synthesized [BMIM][NTF 2 ] IL
functionalized with alkyl amine side chains. Three different ILs are synthesized with
different length of alkyl amine chains namely SAL, MAL, and LAL denoting short,
medium and long alkyl chains as shown below.

In the present work, stable conformers of all the three ILs will be obtained
using DFT. Both VASP and Gaussian09 codes are used for the calculations. The
electronic properties of these three ILs will be examined and results will be presented.
[1] Surya VJ Yuvaraj, Oleg S. Subbotin, Rodion V. Belosludov, Vladimir R.
Belosludov , Kiyoshi Kanie, Kenji Funaki, Atsushi Muramatsu, Takashi
Nakamura, Hiroshi Mizuseki, Yoshiyuki Kawazoe, J. Mol. Liq. 200, 232-237
(2014).
Contact: suryavjy@niche.tohoku.ac.jp

102

Investigation on Pair Stability of Imidazolium Cations with


PGM Chloroanions
Surya V.J. Yuvaraj1,4, Rodion V. Belosludov2, Vladimir R. Belosludov3,4,6, Oleg S.
Subbotin3,4,6 , Ravil Zhdanov3,4,6, Kiyoshi Kanie4, Kenji Funaki4, Atsushi
Muramatsu4,Takashi Nakamura4, and Yoshiyuki Kawazoe1,5
1

New Industry Creation Hatchery Center, Tohoku University, Japan.


2
Institute for Materials Research, Tohoku University, Japan.
3
Nikolaev Institute of Inorganic Chemistry SB RAS, Novosibirsk, Russia.
4
Institute of Multidisciplinary Research for Advanced Materials, Tohoku University,
Japan.
5
Institute of Thermophysics, SB RAS, Novosibirsk, Russia.
In this present work, we have reported on the interaction between two BMIM cations
and two different chloroanions of platinum group metal (PGM) namely, [PdCl 4 ]2- and
[PtCl 6 ]2-. The study involves first principles investigation on the ionic pair stability
between the two entities followed by extraction ability. We have used both
Gaussian09 and VASP codes for total energy calculations.
The binding energies have suggested that both systems are stable.
[BMIM] 2 [PdCl 4 ]2- (Fig. a) is slightly more stable than [BMIM] 2 [PtCl 6 ]2- (Fig.
b) complexes. The increase in intensity of peaks, appearance of new peaks and shift in
peaks are prominent in IR spectrum of both systems and it signifies the interaction of
[BMIM] 2 with [PdCl 4 ]2- and [PtCl 6 ]2- complexes. Partial charge analysis results are in
line with the aforementioned results.

The detailed DFT analysis on the BMIM-metal complexes has revealed that
the complexation of BMIM with metal complexes is successful and they are stable.
One can expect the extraction of Pd and Pt ions since there is active interaction
between BMIM and their respective chloroanions.
Contact: suryavjy@niche.tohoku.ac.jp

103

The thermoelectrochemical effect in Protic Ionic Liquids: A


Molecular Thermodynamic Approach
Mohamad Syafie Mahmood1,2, Suhana Mohd Said1, and Nor Asrina Sairi3

Department of Electrical Engineering, University of Malaya, Kuala Lumpur


Malaysia
2
Faculty of Applied Science, MARA University of Technology, Shah Alam, Malaysia
3
Department of Chemistry, University of Malaya, Kuala Lumpur, Malaysia
The thermoelectrochemical effect is electric potential generation through a redox
reaction due to a temperature difference. The ability of a particular redox mixture to
convert heat into electricity (in units of volts/Kelvin) is quantified by the
electrochemical Seebeck coefficient (S e ). Some well-known examples of redox
couples which exhibit a high S e are CoII/III(bpy) 3 (S e = 1.5- 2.2 mV/K)[1], and
FeII/III(CN) 6 (S e = 1.4 mV/K)[2]. This magnitude of S e is hypothesized by a direct
relation to the entropy difference (S) in a redox couple which its relation is given by
()

= = .
S is the total entropy difference of electronic, vibrational and solvent reorganization
of a molecule that undergoes intermolecular electronic changes. The objective of this
work is to evaluate the Se of a PIL solution from its vibration entropy. In a PIL the Htransfer initiate the redox reaction which drives the entropy in the solution. The H
redox process was broken down into intermediate states which are neutral, neutral to
ionic transition, ionic state and ionic to neutral transition state. Geometrical
optimization of the PIL molecule was carried out using the exchange-correlation
functional theory GGA-PBE. Then,
250
Hessian evaluation was used to
200
compute molecular entropy. From the
150
results, a large S was found between
different states when PIL undergoes H
100
redox
reaction which directly
50
contributes to a large S e . The value of
0
S was found to be up to 200 J/mol.K
0
200
400
600
800
1000
towards 1000 K (Fig. 1). S of this
Temperature (K)
Fig. 1. The S curve of correspond amine order translates into a S e up to 2
against temperature shows larger difference mV/K. This indicates the potential of
of entropy at higher temperature. Inset is the the H redox is theoretically feasible
and produce large value of S e .
triflic acid as anion in PIL.
S (J/mol.K)

[1] T. J. Abraham, D. R. MacFarlane and J. M. Pringle, Energy & Environmental


Science 6 (9), 2639 (2013).
[2] R. Hu, B. A. Cola, N. Haram, J. N. Barisci, S. Lee, S. Stoughton, G. Wallace,
C. Too, M. Thomas, A. Gestos, M. E. Cruz, J. P. Ferraris, A. A. Zakhidov and
R. H. Baughman, Nano letters 10 (3), 838-846 (2010).

Contact: syafiemahmood@siswa.um.edu.my

104

Ab initio random structure searching: Applications to Li


adsorption, hydrogen storage, and dissociation on
monolayer MoS 2
Darwin Barayang Putungan,1,2,3 Shi-Hsin Lin,3 Ching-Ming Wei3 and Jer-Lai Kuo3
1

Department of Physics, National Taiwan University, Taipei, Taiwan


TIGP Nanoscience and Technology Program, Institute of Physics, Academia
Sinica, Taipei, Taiwan
3
Institute of Atomic and Molecular Sciences, Academia Sinica, City, Country
2

The ab-initio random structure searching (AIRSS) is a simple yet powerful tool in
searching for structures via density functional theory calculations [1]. In this work,
we utilized this technique to investigate Li binding on monolayer MoS2, and
hydrogen molecule adsorption on Li-MoS 2 system [2]. Our calculations revealed that
Li can be adsorbed up to full coverage without clustering issues, and a modest
diffusion barrier makes the system essential for battery applications. Molecular
hydrogen adsorption on Li-MoS 2 was found to be stable, up to 4.4 wt% on fullycovered Li configuration. It is further showed that hydrogen molecule can be
dissociated at high Li coverage, with minimal energy barrier. These dissociated
hydrogen atoms can diffuse easily to another site, keeping the reaction sites active. It
is proposed that Li-MoS 2 can be an alternative catalyst to expensive rare noble metals
in hydrogen dissociation reactions.

[1] C. J. Pickard and R. J. Needs, J. Phys.: Condens. Matter 23 (2011) 053201


[2] D. B. Putungan, S. H. Lin, C. M. Wei and J. L. Kuo, Phys. Chem. Chem. Phys.
DOI:10.1039/c5cp00977d
Contact: darwinbputungan@gmail.com

105

Insights into Li-ion Diffusion Mechanisms in Novel


Fluorophosphates Li 9 Mg 3 [PO 4 ] 4 F 3 Cathode Material for
Lithium-ion Batteries: A First Principles Study
Meng-Han Li , Ermias Girma Leggesse , Jyh-Chiang Jiang*
Department of Chemical Engineering, National Taiwan University of Science and
Technology, Taipei, 106, Taiwan, R.O.C

The lithium battery industry is undergoing rapid expansion, now dominating the
power source industry for portable consumer electronics. Since the inception of the
first lithium-ion battery, extensive researches have been made to identify potential
anode, cathode and electrolyte materials in order to attain an improved performance.
In order to be considered as a potential cathode material for lithium-ion battery, a
candidate material need to satisfy certain requirements. Such conditions include, the
stability of the structure during the charge and discharge, high ionic and electrical
conductivity, low cost and high energy density. Among the widely studied cathode
materials, olivine-structured phosphate has received much attention since it offers
high operating voltages, large theoretical gravimetric capacity as well as low cost and
non-toxicity. [1] However, its applicability is limited by its low ionic and electrical
conductivity. Recent studies on Li 2 Fe[PO 4 ]F showed that the intercalation of one Li
atom into LiFe[PO 4 ]F is possible with a reversible and stable capacity of 145 mAh
g1.[2] Similarly, Yahia et al., have synthesized and studied Li 9 Mg 3 [PO 4 ] 4 F 3 which
showed a high ionic conductivity in which a 3D lithium pathway was observed. [3]
In this work, with the aid of density functional theory (DFT) calculations, we
have identified the possible lithium diffusion channels and calculated the energy
barriers for Li-ion diffusion in bulk Li 9 Mg 3 [PO 4 ] 4 F 3 . The effect of localized
electrons, occupied or vacant neighboring Li sites and the change in the channel
dimensions on diffusion are also investigated. As expected, the calculated lattice
parameters, unit cell volume and XRD patterns for Li 9 Mg 3 [PO 4 ] 4 F 3 are in good
agreement with experiment value. The calculated voltage was found to be about 4.6 V
with the volume change of 5.8%. It was found that, Li+ migration through the
pentagonal and hexagonal channels running along the c axis in the bulk plays an
important role in determining the overall ionic conductivity of Li 9 Mg 3 [PO 4 ] 4 F 3 .
Moreover, the Li-ion diffusion observed in the system was not a continuous process
but through a series of jump from one site to another. Based on our calculation, the
migration barrier for the most favorable diffusion path was about 0.74 eV in the
hexagonal channel and about 0.81 eV in the pentagonal channel, which is in a good
agreement with the reported experimental value. [3] The Li-ion diffusion between
pentagonal and hexagonal channel is 0.8 eV. The diffusion behavior happened in the
pentagonal and hexagonal channel at the same time.
[1] Islam, M.S. and C.A.J. Fisher, Chem Soc Rev, 43(1): p. 185-204 (2014).
[2] Recham, N., et al., Chem Mater, 22(3): p. 1142-1148 (2009).
[3] Ben Yahia, H., et al., J Mater Chem A , 2(16): p. 5858-5869 (2014).
Contact: jcjiang@mail.ntust.edu.tw

106

Lithiation Mechanism and Origin of Enhanced Lithium


Storage Capacity for Functionalized Graphene
Nanoribbons : A First-Principles Study
Kun-Han Lin, An Ho, and Chin-Lung Kuo
Dept. Materials Science and Engineering, National Taiwan University, Taiwan

In this study, we employed first-principles calculations to investigate the lithiation


mechanism of functionalized graphene nanoribbons (GNRs) and explore the origin of
their enhanced storage capacity for the anode of Li-ion batteries. Here we have
investigated the Li storage behaviors of various types of functional groups located at
the edge, including -H, hydroxyl, carbonyl and pyrone groups, as well as those lie on
the basal plane like hydroxyl and epoxy groups within different levels of lithiation
and functionalization on the armchair and zigzag nanoribbons, respectively. For
functional groups terminating the edge, our calculated results show that only carbonyl
and pyrone groups can effectively enhance Li adsorption on GNRs, and the most
favorable sites for Li adsorption turn out to be these edged-oxidized groups rather
than the hollow sites on the basal plane. Our calculations further show that the
binding energy of a Li atom can increase with the concentrations of carbonyl/pyrone
groups and Li atoms always prefer to adsorb on these edge-oxidized sites proceeding
through the whole lithiation process. Furthermore, as the carbonyl-terminated GNRs
were fully lithiated, the Li/O atomic ratio was found to be ~1.0, while that for the
pyrone-terminated GNRs was found to be ~0.5, indicating that these edge-oxidized
functional groups can indeed enhance Li storage capacity of GNRs. As for the
functional groups located on the basal plane, the hydroxyl group was found to induce
p-type doping on GNRs, which in turn leads to the increased Li binding energy on the
neighboring hollow sites, and similarly, the epoxy group also exhibits it capability to
enhance Li adsorption on GNRs. Very interestingly, these two functional groups can
serve as the nucleation centers for Li clustering (L3 (OH) cluster for the hydroxyl
group and Li 4 O pyramid for the epoxy groups), which can thereby enhance the Li
storage capacity of GNRs.

Contact: chinlung@ntu.edu.tw

107

Sp2-dominant amorphous carbon film for durable silicon


anodes for lithium-ion batteries
Jeongwoon Hwang,1 Yea-Lee Lee,1 Dongwook Kim,1 Jisoon Ihm,1 Kwang-Ryeol
Lee2, and Seungchul Kim2
1

Department of Physics and Astronomy, Seoul National University, Republic of


Korea
2
Center for Computational Science, Korea Institute of Science and Technology,
Republic of Korea

We investigate structural, mechanical, and electronic properties of graphite like


amorphous carbon coating on bulky silicon to examine whether it can improve the
durability of silicon anodes of lithium-ion batteries, using molecular dynamics
simulations and ab initio electronic structure calculations. Structural models of carbon
coating were prepared using molecular dynamics simulations of atomic carbon
deposition with low incident energy (1-16 eV). As lower the incident energy, ratio of
sp2 carbons increases while that of sp3 decreases, and the carbon films become more
porous. The films prepared with very low energy satisfies the conditions of durable
anodes; it contains lithium ion conducting channel, is electrically conducting to
supplement poor conductivity of silicon, can restore its structure after large
deformation to accommodate the volume change during the operations. Through this
study we suggest graphite-like porous carbon coating on silicon will extend the life
time of silicon anodes of lithium-ion batteries.

Contact: sckim@kist.re.kr

108

The Effect of Different Substitution on Bis(trifluoroborane)benzimidazole Lithium Salts for Battery Electrolytes
Tun Sriana, Ermias Girma Leggesse, and Jyh-Chiang Jiang
Department of Chemical Engineering, National Taiwan University of Science and
Technology, Taipei, Taiwan
LiPF 6, which is a commonly used electrolyte salt, offers electrolyte solutions with
a good electrochemical stability, a superior ion conductivity and thermal stability
when dissolved in binary or ternary solvent systems of cyclic carbonates.[1] However,
LiPF 6 can undergo autocatalytic decomposition into LiF and PF 5 at elivated.[2],[3]
Recently, in order to curcumvent the known problems of this salt, designing lithium
salt by considering substituted heterocyclic anion have been reported. In this work,
we used bis(trifluoroborane)-benzimidazole (BTB-) as parent structure and identify
potential anion candidates by using density functional theory (DFT) calculations.
New anion structures were proposed by considering posible substitution at the C5
position by electron donating (NH 2 , -OCH 3 , -CH 3 ) and withdrawing group (-CF 3 , CN, -NO 2 ). After that, -CH 3 or NO 2 substituted on C2 is combined with molecule
donating and withdrawing group on C5, C6, and C7 to generate derivatives of BTB-.
The influence of different substitutituents on ion pair dissociation energies and
oxidation potentials of the molecules were investigated. Based on our calculation, we
have found that the position and type of substituent on the parent structure
significantly influences the ion dissociation energies and oxidation potentials.
Compared to introduction of electron donating groups, electron withdrawing groups
result in an increase in anion oxidation stability. The most promising anion were
generated by considering electron withdrawing group substitution at C2, C5 and C7
positions.
Among
the
possible
anions,
bis(trifluoroborane)-2,5,7trinitrobenzimidazole with calculated oxidation potential of 5.95 V vs. Li+/Li, can be
a promising candidate for high voltage lithium ion battery.
[1] K. Xu, Chem. Rev. 104, 4303 (2004).
[2] U. Heider, R. Oesten, and M. Jungnitz, J. Power Sources 81-82, 119 (1999).
[3] C.G. Barlow, Electrochem. Solid-State Lett. 2, 362 (1999).

Contact: jcjiang@mail.ntust.edu.tw

109

The Influence of Chloride Ions Preference Adsorption on Al 2 O 3 (0001) Surface


Chuan-Hui Zhang*, Min Liu, Ying Jin, Dong-Bai Sun
National Center for Materials Service Safety, University of Science and
Technology Beijing, Beijing, China
Conductor-like screening model (COSMO), Periodic DFT calculations have been
performed on a Al 2 O 3 surface to model the influence of preference adsorption and
interaction of chloride ions at increasing monolayer coverage on undefective passive
film on Aluminum in solution environment. The results evidence that the critical
monolayer of Cl- is 3/7, which is redefined. With increasing Cl- adsorption, both the
first and second Cl- move from Al(1) atop and bridge10 sites to O(5) sites, suggesting
that the weaker interaction between Cl- and Al 2 O 3 surface but stronger interactions
between three ions make the electrons uniformly occupy on the energy levels of them.
More calculations shows that the preference adsorption sites of Cl- are independent of
the surface area of oxide, and the adsorption energy decrease in three steps, each
adsorption energy step only relate to the adsorption site and the morphology. On
undefective oxide film, low coverage Cl- adsorption would restrain surface
breakdown to happen which is consistent with the experiment results. [1,2]

[1] P.M. Natishan, and W.E. O'Grady, J Electrochem. Soc. 161 C421 (2014).
[2] J. Soltis, Corros. Sci. 90 5 (2015).

Contact: *Corresponding author. E-mail address: zhangch@ustb.edu.cn

110

Theoretical Insights into the Effect of Water on the


Oxidative Decomposition of Propylene Carbonate in
Lithium Ion Batteries
Ting -Yin Chen, Ermias Girma Leggesse and Jyh - Chaing Jiang
Department of Chemical Engineering, National Taiwan University of Science and
Technology, Taipei, Taiwan
The Lithium-ion rechargeable batteries are widely used in portable electronic devices
as compared to the conventional batteries due to their high energy density and good
environmental properties. However, there are still many challenges concerning the
safety requirements. Propylene carbonate (PC) and lithium hexafluorophosphate
(LiPF 6 ) have been extensively studied as electrolyte compositions for lithium ion
battery. [1] At open-circuit and during cell charge, the high potentials of several
cathode materials may result in electrolyte oxidation. These highly exothermic
electrolyte decomposition reactions are usually accompanied by the decomposition of
the cathode material and gas evolution that will cause potential danger and reduced
cyclic stability. [2] The presence of trace amount of water is also believed to enhance
the electrolyte decomposition reactions. In this study, density functional theory is
applied to investigate the oxidative decomposition mechanisms of PC/LiPF 6 in the
presence of water. The solvent effect is included using the implicit Solvation Model
with Density method. Based on the calculation, there is a significant difference in the
oxidative decomposition mechanism of [H 2 O-PC-PF 6 ]- compared to [PC-PF 6 ]- . For
the [PC-PF6]- , HF is formed at the initial oxidation step; whereas, in [H 2 O-PC-PF 6 ]the elementary oxidation reactions, such as H 3 O+ formation and C-C bond-breaking,
happen depending on the position of water. The energy barrier for the ring-opening
step of [PC-H 2 O-PF 6 ] was found to be much lower than that of [PC-PF 6 ]. Our
calculations suggest that, the initial oxidative decomposition products of PC in the
presence of water are acetone radical, propionaldehyde radical and carbon dioxide. In
agreement with experimental observation [3], the final products were found to be
acetone, propionaldehyde, and 2-ethyl-4-methyl-1, 3-dioxolan.
[1] Xing L., Wang C., Li W., Xu M, Meng X., Zhao S., J. Phys. Chem. B 113,
5181 5187 (2009).
[2] Leggesse E. G., Lin R. T., Teng T. F., Chen C. L., Jiang J. C.*, J. Phys. Chem.
A 117, 7959 7969 (2013).
[3] Ufheil J., Wursig A., Schneider O D, Novak P., Electrochemistry
Communications 7, 1380 1384 (2005).

Contact: jcjiang@mail.ntust.edu.tw

111

High-Throughput Virtual Screening of Sulfone-Based


Electrolytes for High-Voltage Li-Ion Batteries
Ting-Yi Wei, Ermias Girma Leggesse, Jyh-Chiang Jiang
Department of Chemical Engineering, National Taiwan University of Science and
Technology, Taipei, 106, Taiwan, R.O.C
Even though the demand for novel materials with specific properties increases
significantly, the search for materials using experimental procedures is hindered by
high costs and time-consuming procedures of synthesis. An alternative and new
approach is to use theoretical methods to systematically design and screen
components within a short period. Recent studies indicate that sulfone-based
electrolytes have a great potential to for lithium-ion cells using high-voltage cathodes.
Some of the desired properties of unsymmetrical ethyl methyl sulfone (EMS) include
anodic stability, high dielectric constant and boiling point. [1]
In this work, virtual molecular structure library, consisting of 264 compounds, based
on EMS as a core structure were generated by employing R-group enumeration
scheme using ChemAxon. The selected R-groups were included strong, moderate and
weak functional groups. High throughput computational screening using Pipeline
Pilot 9.1.0 was then carried out to identify potential solvents derived from EMS.
Molecular properties were selected as descriptors relative to EMS and calculated
using the PM6 semiempirical quantum method. To illustrate the potential selected
molecules and the screening technique, we apply density functional theory (DFT)
method to compute some specific properties of each molecule and compared with
EMS. Among the screened candidates, fluorinated and cyano solvents, showed better
oxidative stability (>7V), broad electrochemical window (>10.0eV). Moreover, other
molecular properties such as chemical hardness, electron affinity, ionization potential,
were found to be better than EMS. One-electron reductive and oxidative
decomposition reaction mechanism studies for selected candidates were also
performed and compared with EMS.
[1] Islam, M.S. and C.A.J. Fisher, Chem Soc Rev. 43, 1 185 (2014)
[2] Recham, N., et al., Chem Mater. 22, 3 1142 (2009)
Contact: jcjiang@mail.ntust.edu.tw

112

Ab-initio Study for Dopant Effects on the Lithiation


Processes of c- Si
Han-Hsin Chiang, Chin-Lung Kuo*
Department of Materials Science and Engineering, National Taiwan University, Taipei,
Taiwan
Abstract
In this study, we employed first-principles calculations in conjunction with molecular
dynamics simulations to investigate the effects of chemical doping on the lithiation kinetics of
crystalline Si during the electrochemical processes. Our ab-initio molecular dynamics
simulations showed that the lithiation processes of c-Si can be substantially enhanced by
phosphorus-doping while that was not the case for the boron-doped Si electrodes in
comparison with that for the undoped Si. Our calculations further showed that the
substitutional boron atom can help the insertion of Li ions into the Si matrices but
phosphorus-doping appears to increase the insertion barrier of Li ions instead. Although the
diffusion energy barriers of Li ions may increase (decrease) slightly in the boron
(phosphorus)-doped Si matrices, these changes were found to be highly-localized within the
range of the nearest-neighbor distances. Furthermore, our calculated mechanical response of
the Li-inserted Si matrices showed that the phosphorus-doped Si matrices can become more
ductile and more easily undergo plastic deformation upon hydrostatic stress, but on the
contrary, the Si matrices may become more brittle and stiffer in nature as it was doped with
boron atoms. These results indicated that mechanical softening of the Si bond network can be
the major reason that leads to the enhanced lithiation kinetics of c-Si by phosphorus-doping.
Key words: Si-based anode materials, lithiation, density functional theory, molecular
dynamics

Contact: chinlung@ntu.edu.tw

113

Spin Torque Effect in BeO-based Magnetic Tunnel Junction


Fa-Chieh Cju ()1 and Yu-Hui Tang () 1*
1

Department of Physics, National Central University, Jhong-Li, Taiwan

The giant tunnel magnetoresistance (TMR) [1] and the spin transfer torque (STT)
effect [2] in MgO-based magnetic tunnel junctions (MTJs) have attracted intensive
studies for applications in nonvolatile magnetic random access memories and
magnetic sensors, resulting from the highly spin-polarized density of states on both
left and right FM/MgO interfaces [3], where FM denotes ferromagnetic materials.
The success of MgO-based MTJs points out an important clue for finding alternative
central materials in MTJs.
In this study, the spin transport properties of Co/BeO/Co junctions have been
studied by the first-principles calculation with the non-equilibrium Keldysh Greens
function method. For the first time, we predict that BeO-based magnetic tunnel
junctions exhibit large values of both TMR and STT by tailing its magnetic
configurations between two Fe electrodes. The underlying mechanism can be
understood by the strong (weak) spin-polarized density of states at Co/O (Co/Be)
interface, due to the large (small) electronegativity difference between Fe and O (Be)
ions. The highly asymmetric bias behavior of both TMR and STT also can be found.
Our results suggest that BeO-based MTJ can be a possible candidate for MRAM
applications. This work is supported by the National Science Council of Taiwan
(Contract No. NSC99-2112-M-008-020-MY3)
[1] S. Ikeda et al., Appl. Phys. Lett. 93, 082508 (2008).
[2] C. Wang et al., Nature Phys. 7, 496 (2011).
[3] W. H. Butler et al., Phys. Rev. B63, 172407 (2001)

114

Quantum transport properties of Au/oligothiophene/Au


single molecular junctions: A first-principles study
Cheng-Wei Ku ()1, Yu-Hui Tang () 1*, and C. C. Kaun () 2*
1

Department of Physics, National Central University, Jhongli, Taiwan 32001


Research Center for Applied Sciences, Academia Sinica, Taipei 11529, Taiwan

Controlling molecules to create desired transport properties in an electronic


nanodevice is a promising way toward nanoelectronics. Lately, we have investigated
the conductance switching properties during the stretching of Au/oligothiophene
dimethylene dithiol/Au single molecule junctions [1] by the first-principles method
with the non-equilibrium Green's function approach, which are in agreement with the
experimental measurements and observations [2]. In this study, the first-principles
calculation is employed to give a comprehensive understanding of the current-voltage
(I-V) characteristics in 3T1DT (with three thiophene rings) and 4T1DT (with four
thiophene rings) cases. At the breaking point, the highest occupied molecular orbital
(HOMO) of longer 4T1DT is closer to the Fermi energy so that the 4T1DT is more
conductive than is the shorter 3T1DT. When the applied bias is nonzero, the
transmission peak resulting from the HOMO level is shifted with the chemical
potential of right electrode. With discrepant shifting rates of projected density of
states(PDOS) of molecule and electrode at the junction break, the I-V curve
characters highly asymmetric and stepped characteristics for both cases. Once this
transmission peak is included in the bias window, the abrupt enhancement of current
can be found at lower (higher) bias for 4T1DT (3T1DT) case.

[1] Y. H. Tang et al., J. Phys. Chem. C 115, 25105 (2011).


[2] B. Q. Xu et al., Nano Lett. 5, 1491 (2005).
Contact: yhtang@cc.ncu.edu.tw and kauncc@gate.sinica.edu.tw

115

Dispersive Charge Trasport Study in Periodic Structures of


Crytalline- Amorphous Hybrid Organic Materials
K.Y. Choo,1,2 S.V. Muniandy,1 K.L. Woon,1 M.T. Gan2 and D.S. Ong2
1

Department of Physics, Faculty of Science, University of Malaya, 50603 Kuala


Lumpur, Malaysia
2
Faculty of Engineering, Multimedia University, Jalan Multimedia, 63100
Cyberjaya, Selangor, Malaysia

Transport dynamics of unipolar charge carriers in periodic crystalline-amorphous


organic material is studied using the time-fractional drift-diffusion equation with
variable order (VO-TFDDE). Implicit finite difference scheme and centered finite
difference scheme are employed to discretise the time-fractional derivative operator
and spatial derivative operator of VO-TFDDE [1-2]. The VO-TFDDE is then solved
numerically using explicit time marching method, while the corresponding electric
field is solved using self-consistent Poisson solver. Charge carriers are found to
propagate faster through the purely crystalline and periodic crystalline-amorphous
materials while preserving its localized carrier density. In contrast, significant
broadening of carrier density and longer transit time are seen in the case of purely
amorphous structure. This study suggests a strategy to reduce the spread of carrier
density by introducing periodic sandwiching of crystalline and amorphous structure
in organic semiconductor materials.

References:
[1] Y. Lin and C. Xu, J. Comp. Phys. 225, 1533 (2007).
[2] H. Sun, W. Chen, C. Li, and Y. Chen, Int. J. Bifurcation Chaos 22, 1250085
(2012).

Acknowledgement: The authors are grateful to the University of Malaya for PRPUM Grant
(CG010-2013) and Multimedia University for financial support.
Contact: Kan Yeep, CHOO, Email: kychoo@mmu.edu.my

116

Effects of different adsorption modes of sensitizers on TiO 2


on the dye loading, absorption spectra and electron injection
properties in dye-sensitized solar cells: A DFT/TD-DFT
study
Jia-Cheng Hu and Hui-Hsu Gavin Tsai*
Department of Chemistry, National Central University,
Jhongli District, Taoyuan City, Taiwan
E-mail: hhtsai@cc.ncu.edu.tw
The working principle of DSCs is light-harvesting processes similar to those
of the photosynthetic system in nature. Dye sensitizers play a key role in lightharvesting efficiency. It is known that the dye loading of dyes on TiO 2 will affect the
light-harvesting efficiency. Recent work (JACS, 2015) using X-ray reflectivity shows
some dyes with cyanoacrylic acid anchoring group are not aligned with their
molecular long axes perpendicular to the substrate plane (tilt angle = 0) on the TiO 2
substrates, instead exhibit significant tilt angles from the surface normal of ~70. This
result indicates the dyes with cyanoacrylic acid anchoring group may adsorbed on
TiO 2 substrates with different binding modes rather than the commonly accepted
bidentated modes using carboxylic group.
In this study, we employed density functional theory (DFT) and timedependent DFT (TD-DFT) to invesigate the effects of possible adsorption modes of
dyes with cyanoacrylic acid anchoring group on TiO 2 on dye loading. In particular,
we focus on the TPA-T-TTAR-A and TPA-TTAR-T-A1 with similar molecular
structure, but with different tilt angles as well as dye loading on TiO 2 . Taking the
conformations of TPA-T-TTAR-A and TPA-TTAR-T-A and their adsorption modes
into consideration, our calculations are able to distinct their experimentally observed
tilt angles Furthermore, we investigate the the effects of possible adsorption modes on
the absorption spectra and electron injection properties.

(1)
Nanjia Zhou , K. P., Byunghong Lee , Sheng Hsiung Chang , Boris
Harutyunyan, Peijun Guo, Melanie R. Butler, Amod Timalsina, Michael J. Bedzyk,
Mark A. Ratner, Sureshraju Vegiraju, Shuehlin Yau, Chun-Guey Wu, Robert P. H.
Chang, Antonio Facchetti, Ming-Chou Chen, Tobin J. Marks 2015, 137, 4414.

117

Theoretical Calculations on Photochemistry of Irgacure 907


(2-Methyl-4-(methylthio)-2-morpholinopropiophenone) and
Newly Designed Photoinitiator
Wan-Rou Tong, Ermias Girma Leggesse, Jyh Chaing Jiang
Department of Chemical Engineering, National Taiwan University of Science and
Technology, Taipei, Taiwan

A photoinitiator is a compound that undergoes a photoreaction upon absorption


of light, producing reactive species that are capable of initiating chemical reactions
and cause photo-polymerization. Irgacure 907 (2-Methyl-4-(methylthio)-2morpholinopropiophenone) is a highly efficient type I -aminoketone photoinitiator
that is widely used to initiate the photopolymerization of chemically unsaturated
prepolymers.
In this work, the photocleavage reaction mechanisms as well as excited state
properties and the underlying relaxation mechanisms upon photoexcitation of
Irgacure 907 is studied by using DFT calculations. To investigate the mechanisms,
the excited singlet and triplet states were considered in detail. Based on our
calculations, we have found that the radical formation for Irgacure 907 originates
from the triplet states, which is typical of type I photoinitiators. As expected, after
excitation, the photoinitiator undergo rapid intersystem crossing (ISC) which is an
important step in the overall process. In addition to the observed change in the orbital
angular momentum, the smallest energy gap was found to be between S2 and T1.
New photoinitiators, based on Irgacure 907, were also designed, and their
photochemical properties have also been investigated in details.

[1] Thomas J. A. Wolf, Dominik Voll, Christopher Barner-Kowollik, AndreasNeil Unterreiner, Macromolecules. 45, 22572266 (2012).
[2] M. Buback, A. Kuelpmann, Macromolecules. 204, 632-637 (2003).
Contact: jcjiang@mail.ntust.edu.tw

118

A density-functional theory study of the opto-electronic


properties of polymorphic WO 3
Tae-Hun Lee, Yong-Hyuk Lee, Woosun Jang, and Aloysius Soon
Global E3 Institute and Department of Materials Science and Engineering,
Yonsei University, Seoul, South Korea

Despite the technological importance of tungsten oxide (WO 3 ) in various modern-day


applications, e.g. photocatalysis in solar cells and nanosensors, relatively few
systematic theoretical studies of polymorphism on various physio-chemical properties
have been devoted to this material system [1-3].
Bulk WO 3 exhibits different polymorphic phases, namely the monoclinic, triclinic, cmonoclinic, orthorhombic, tetragonal, and hexagonal phases, with increasing
temperature. It is commonly accepted that at room temperature, WO 3 adopts a
monoclinic lattice. But recently, many experimental results demonstrate the
manifestation of various interesting temperature-controlled nanomorphologies of
WO 3 , which is believed to have originated from the different polymorphs of WO 3 [46].
In this work, using density-functional theory calculations, we investigate and study
the various opto-electronic properties which will most likely be strongly affected by
the poylmorphic state that WO 3 adopts. We pay particular attention to the explicit
approximations (ranging from the (semi)local to the range-separated hybrids) to the
exchange-correlation functional to afford a more accurate description of these optoelectronic properties of WO 3 .

[1] Q. Chen, J. Li, X. Li, K. Huang, B. Zhou, W. Cai and W. Shangguan, Environ. Sci.
Technol., 46, 11451 (2012)

[2] X. Li, J. Bai, Q. Liu, J. Li and B. Zhou, Sensors, 14, 10680 (2014)
[3] X. Zhang, D. Chandra, M. Kajita, H. Takahashi, L. Dong, A. Shoji, K. Saito,
T. Yui, M. Yagi, Int. J. Hydrogen Energy., 39, 20736 (2014)
[4] H. Simchi, B. E. McCandless, T. Meng, W. N. Shafarman, J. Alloys Compd.,
617, 609 (2014)
[5] Y. Choi, S. Kim, M. Seong, H. Yoo, J. Choi, Appl. Surf. Sci., 324, 414 (2015)
[6] N. Wang, D. Wang, M. Li, J. Shi, C. Li, Nanoscale, 6, 2061 (2014)

Contact: Aloysius Soon (aloysius.soon@yonsei.ac.kr)

119

Structural and Bonding Properties of AuSi n - (n=4-12) and


AuGe n - (n=2-12) Clusters: Photoelectron Spectroscopy and
Density-Functional Calculations
Hong-Guang Xu,* Sheng-Jie Lu, Gang Feng, Xiao-Jiao Deng, Xi-Ling Xu,
and Wei-Jun Zheng *

Beijing National Laboratory for Molecular Sciences, State Key Laboratory of


Molecular Reaction Dynamics, Institute of Chemistry, Chinese Academy of Sciences,
Beijing 100190, China

Transition metal-doped silicon/germinum semiconductor clusters have been studied


extensively with experiments[1-3] and theoretical[4,5] calculations because they have
novel properties and may serve as the building blocks for the fabrication of new
semiconductor nanostructures. In this work, we conducted a combined anion ion
photoelectron spectroscopy and density functional theory study on the structural
evolution of gold-doped semiconductor cluters, AuSi n - (n=4-12) and AuGe n - (n=212). For AuSi n - (n=4-12) clusters, our results suggest that their structures are all
dominated by exohedral structures with the Au atom connecting to the vertex, edge or
surface of bare Si n cluster. No endohedral structure has been found for AuSi n - clusters
with n 12. For AuGe n - (n=2-12) clusters, we found that the low-lying isomers of
AuGe n - with n 11 are dominated by endohedral structures, those of AuGe n - with n
< 11 are dominated by exohedral structures. The most stable structure of AuGe 11 - is a
twisty bicapped pentagonal antiprisms structure.

[1] C. Author, D. Author, and E. Author, Phys. Rev. Lett. 100, 123 456 (2012).
[2] A. Grubisic, Y. J. Ko, H. P. Wang, and K. H. Bowen, J. Am. Chem. Soc. 131,
10783 (2009).
[3] V. T. Ngan, P. Gruene, P. Claes, E. Janssens, A. Fielicke, M. T. Nguyen, and
P. Lievens, J. Am. Chem. Soc. 132, 15589 (2010)
[4] L. Z. Kong, and J. R. Chelikowsky, Phys. Rev. B 77, 073401 (2008)
[5] X. J. Li and K. H. Su, Theor. Chem. Acc. 124, 345 (2009)

Contact: xuhong@iccas.ac.cn (H.-G. Xu) zhengwj@iccas.ac.cn (W.-J. Zheng)

120

Anharmonicity Calculation of OH Stretching Motion in


Small Methanol Clusters along Normal Coordinates
Hsiao-Han Chuang1, Jer-Lai Kuo2, Kaito Takahashi2, Asuka Fujii3
1

Department of Chemistry, National Taiwan University, Taipei, Taiwan.


Nano Science and Technology Program, Taiwan International Graduate Program.
2
Institute of Atomic and Molecular Sciences, Academia Sinica, Taipei, Taiwan.
3
Department of Chemistry, Graduate School of Science, Tohoku University, Sendai,
Japan

Tagging messengers (usually stable atoms or molecules) on large ionic clusters can
deliver the vibrational infrared spectra of the bare system well, because charges
delocalize better [1]. Nevertheless, in the small clusters, they perturb the system by
themselves and would not act as a messenger anymore. Infrared Pre-Dissociation
(IR-PD) spectra of the mass-selected ionic cluster H+(CH 3 OH) 13 Ar 02 were observed,
and Ar perturbed the OH stretching motion between 2800 to 3800 cm1.
The observed sharp peaks were analyzed with theoretical simulations in reduced
dimension. We scaned the potential energy surface along several selected normal
coordinates, and constructed the kinetic operator by 11-point finite difference method.
The peak around 3600 cm1 majorly comes from the free OH stretching contrubution,
and the other peak has more features of Ar-bonded OH stretching, see the figure
below. The simulated spectra by using B3LYP/6-31+G(d,p) to calculate the
fundamental transition of covalent bonds were in agreement with experimental results,
but overestimated the interaction between messengers and ionic protonated methanol
clusters.

[1] Okumura, M.; Yeh, L.I.; Myers, J.D.; Lee, Y.T. J. Phys. Chem., 94, 3416 (1990).
hhchuang@phys.sinica.edu.tw

121

An Ontological Account on the Spectral Signatures of an


Ionic Hydrogen Bond in Some Zundel Type Structures
Jake A. Tan,1,2,3 and Jer-Lai Kuo1,3
1

Institute of Atomic and Molecular Sciences, Academia Sinica, Taipei, Taiwan


Department of Chemistry, National Tsing Hua University, Hsinchu, Taiwan
3
Molecular Science and Technology Program, Taiwan International
Graduate Program, Academia Sinica, Taipei, Taiwan

It has been widely recognized that Ionic Hydrogen Bond (IHB) plays a significant
role in enzymatic catalysis, acid-base reactions and several processes in the
atmosphere. Over the last few decades, there had been an interest on clusters
involving IHBs. Spectroscopic techniques like Infrared Multiple-Photon Dissociation
(IRMPD) and Infrared Predisociation (IRPD) are used to probe their vibrational
signatures [1]. In this study, we have chosen proton bound dimers of MeOH and
Me 2 O as model systems in understanding the vibrational signature of an IHB. By
adopting a reduced dimensional approach, key normal mode vibrations were chosen.
The potential was constucted by scanning normal mode displacement vectors using
MP2/aug-cc-pVDZ. It was found out that IHB stretch strongly couples with flanking
group motions. The task of assigning the spectral lines was found to be nontrivial due
to the entanglement of the normal modes. Lastly, a comparison between the
experimental spectrum independently measured by both Fridgens and Johnsons is
discussed [2]-[3].

[1] L. I. Yeh, M. Okumura, J. D. Myers, J. M. Price and Y. T. Lee, J. Chem. Phys.


91, 7319(1989).
[2] J. R. Roscioli, L. R. McCunn and M. A. Johnson, Science 316, 249 (2007).
[3] T. D. Fridgen, L. MacAleese, P. Maitre, T. B. McMahon, P. Boissel and
J.
Lemaire, Phys. Chem. Chem. Phys. 7, 27472755 (2005).

Contact:
jaketan@gate.sinica.edu.tw
jlkuo@pub.iams.sinica.edu.tw

122

Negative temperature dependance of atmospherically


significant R 1 R 2 COO+ Water reaction.
Liang-Chun Lin1,2 Kaito Takahashi2
1
Institute of Atomic and Molecular Sciences, Academia Sinica, Taipei, Taiwan
2
Department of Chemistry, National Taiwan University, Taipei, Taiwan
Atmospherically relevant R 1 R 2 COO, so-called Criegee intermediates(CIs), includes
simplest (R 1 =R 2 =H), mono-, ethyl-, and dimethyl- substituted CIs. These strong oxidizing
species are the key intermediate in the ozonolysis of different kinds of alkenes. Alkenes are
released to the troposphere in very large amounts from biogenic and anthropogenic sources.
[1] CIs reactions with atmospheric abundant water vapours is considered to be a very
important issue in atmospheric chemistry research. To uderstand these processes, we consider
CIs + H 2 O and CIs + (H 2 O) 2 reactions, ignoring CIsreactions with bigger H 2 O clusters.
Based on our calculation result, for atmospheric implication, CIs + (H 2 O) 2 dominate the
reaction on CIs + water vapour over CIs + H 2 O in cold upper troposphere layer even though
[(H 2 O) 2 ] is much lower than [H 2 O]. From the different trend in reactivity, discussed below,
CIs + H 2 O reactions originally regarded very slow in room or lower temperature, actually
play significant roles at high temperatures.
In our research, we separated the whole reaction pathways into 2 parts: VDW (Van Der
Waals) complexes formation and reactions of VDW complexes to products. The thermal
equilibrium constants and rate constants were calculated using the Thermo program in the
Multiwell program suite. The relative energies, for the reactant, VDW complex, transition
state and the product were obtained by the complete basis set extrapolation using the
QCISD(T) method with the Dunning basis at the geometries calculated by B3LYP/6311+G(2d,2p). The harmonic and anharmonic vibrational frequencies wer also obtained at
B3lYP level.
On the basis of our calculations at different temperatures
273.15 K, P H2O =16 Torr, k H2O *[H 2 O] = 31 sec-1 and k (H2O)2 *[(H 2 O) 2 ] = 23952 sec-1;
298.15 K, P H2O =16 Torr, k H2O *[H 2 O] = 43 sec-1 and k (H2O)2 *[(H 2 O) 2 ] = 4416 sec-1;
373.15 K, P H2O =16 Torr, k H2O *[H 2 O] = 102 sec-1 and k (H2O)2 *[(H 2 O) 2 ] = 110 sec-1.
For CIs + H 2 O reactions, total rate constants go up when temperature goes up; whereas for
CIs + (H 2 O) 2 case, total rate constants go down when temperature goes up. This opposing
trend in the total rate constants comes from the fact that VDW complexes formation parts
dominate the whole reactions for CIs + H 2 O system, and reactions of VDW complexes to
products dominate the whole reactions for CIs + (H 2 O) 2. The phenomena can be fully
described by the potential energy surface diagram seen below.
[1] M. T. Benjamin, M. Sudol, L. Bloch and A. M. Winer, Atmos. Environ., 1996, 30, 1437

Contact: ilikejenny920729@gmail.com

CH2OO +H2O TS

CH2OO +(H2O)2 TS

123

Theoretical Study of the Acousto-Optic Low Frequency


Resonance-like Vibration Behaviour in the High Density
Amorphous Ice
Gets K.V.1,4, Belosludov V.R.1,4, Subbotin O.S.1,4,
Belosludov R.V.2 and Kawazoe Y.3,4
1

Nikolaev Institute of Inorganic Chemistry; SB RAS, Novosibirsk, Russia


2
Institute for Materials Research, Tohoku University, Sendai, Japan
3
New Industry Hatchery Center, Tohoku University, Sendai, Japan
4
Kutateladze Institute of Thermophysics, SB RAS, Novosibirsk, Russia

In this study we present the research of acousto-optic resonance-like


behaviour of vibration modes in high density amorphous ice (HDA). The stable cubic
model of HDA ice containing 512 rigid water molecules was constructed using the
molecular dynamics and conjugate gradient methods. A modified SPC/E potential:
short-range interaction was described by the van-der-Waals forces, long-range
interaction was described by the Coulomb forces. The approach [1], which considers
the model cell as a unit cell of the pseudo-crystal was applied (taking into
consideration the periodic boundary conditions of HDA ice model cell). Conjunction
of this approach and the lattice dynamics method allows us to calculate the dynamical
characteristics of HDA ice structure along the Brillouin zone of pseudo-crystal.
The results of simulation work along the Brillouin zone of pseudo-crystal let
to construct the dispersion curves of HDA ice which show the resonance-like
behaviour of longitudinal acoustic vibration curve and lowest energy crystal-like [2]
optic vibration curve. Increase of participation ratio (growth of molecular amplitudes
and number of involved molecules) of vibrations close to resonance-like convergence
of vibration modes observed. Study of calculation of dynamic structure factor show
the good agreement with experimental data [3] for HDA ice in [3 meV; 25 meV]
region.
The reported study was supported by RFBR, research project No. 14-0231105 mol_a.
[1] G.S. Grest et al., Phys. Rev. Lett. 29 (17), 1271 (1982).
[2] K.V. Gets et al., Int. J. Comp. Mat. Sci. Eng. 1, 1250008 (2012).
[3] M.M. Koza et.al., Phys. Rev. B 77, 104306 (2008).

Contact: gets@niic.nsc.ru

124

Hydration Water Behavior Characterization


by Simulation-Based Data-Mining Approach
Taku Mizukami,1 Nguyen Viet Cuong,2 Ho Tu Bao,3 and Dam Hieu Chi3
1

School of Materials Sciences, JAIST, Ishikawa, Japan


2
HPC systems Inc., Tokyo, Japan
3
School of Knowredge Sciences, JAIST, Ishikawa, Japan

Water plays an important role in solute-solvent system in materials science field,


especially on biological molecules. A large number of biomolecules express their
functions in a hydrated environment, and their functions have mechanisms that are
strongly correlated with water interactions [1]. However, the large-local fluctuation
motion and the flip-flop type energy exchanges of water molecule make difficult to
quantitatively evaluate water dynamics [2].
We present a simulation-based data-mining approach that enables quantitative
analysis for the dynamical structure of water. We focus on the motive behavior of all
water molecules observed in the classical molecular dynamics simulation systems,
along with the description of the dynamical structure of water molecules. Through a
data-mining approach and clustering techniques [3], the atomistic level motion of an
individual water molecule is categorized in the context of the water molecules
behavior.
Classical molecular dynamics (MD) simulations of the pure water and the proteinwater systems at room temperature were executed by means of Amber11 program
package. The trajectory data of individual water molecule was preprocessed by the
mixture model and transferred into the multidimensional designed feature space.
After classification of all the water molecules on the feature space, several classes of
the water molecule behavior were isolated. The projection of the class from the
feature space into the MD Cartesian space reproduces protein hydration water with
following molecular characteristics. (1). Water-protein radial distribution function.
(2). Three dimensional distribution of classified water indicates hydration sites of
protein. (3). Interactions between hydrophobic and/or hydrophilic surface of protein
and water.
These results show that our method is a promising strategy for the quantitative
characterization of the structure and dynamics of water in the solute-solvent system.
[1] V. Helms, Chem. Phys. Chem. 8, 23-33 (2007).
[2] I. Ohmine, H. Tanaka, P. G. Wolynes, J. Chem. Phys. 89, 5852-5860 (1988).
[3] Data-Mining 2nd ed. I. H. Witten, E. Frank, Elsevier (2005).
Contact: mizukami@jaist.ac.jp

125

Molecular Dynamics Simulations of Polyethylene Glycol


Monolaurate in Water and in Aliphatic Alcohols
Ianatul Khoiroh,1 Mohamed Taha,2 and Ming-Jer Lee3
1

Department of Chemical & Environmental Engineering, University of


Nottingham Malaysia Campus, Semenyih, Malaysia
2
Department of Chemistry, University of Aveiro, Aveiro, Portugal
3
Department of Chemical Engineering, National Taiwan University of Science
and Technology, Taipei, Taiwan

We explored the structural and dynamical properties of polyethylene glycol


monolaurate (PEGML) in water and in various aliphatic alcohols (methanol, ethanol,
2-propanol, 2-butanol, tert-butanol, and 1-pentanol) by means of molecular dynamics
simulations. The PEGML and the alcohols were simulated using the OPLS-AA
(optimized potentials for liquid simulations, all-atom) force field and water using the
SPC/E (extended simple point charge) model. To gain more insight to the solution
behaviour between the PEGML and the solvent molecules at the molecular level, we
analysed the radial distribution functions. From the isothermal-isobaric (NPT,
constant number of particles, constant pressure, and constant temperature) ensemble,
we extracted the densities for simulated systems and compare the values to those from
experimental results in order to confirm the validity of the selected force fields. The
densities from MD simulations are in good agreement with the calculated values
obtained from the experiment. To gain more insight to the nature of interactions
between PEGML molecule and solvents, we analyzed the hydrogen-bonds, the
electrostatic (Couloumb) interactions, and the van der Waals (Lennard-Jones)
interactions energies extracted from MD simulations. The results were further
strengthened by computing the solvation free energy by employing the free energy
perturbation (FEP) approach. In this method, the free energy difference was computed
by using the Bennet Acceptance Ratio (BAR) method. Moreover, the radial
distibution functions were analyzed in order to gain more understanding of the
solution behavior at the molecular level. Dynamic aspect of the mixture behavior is
inferred from the calculated shear viscosity which was computed by using nonequilibrium molecular dynamics (NEMD) simulations.

Contact: Ianatul_Khoiroh@nottingham.edu.my

126

Hydration and Thermal effects on Structure and Dynamic


Properties of Mono- and Guerbet Branched-chain -DMaltosides: An Atomistic Simulation Study
Vijayan ManickamAchari1, Richard A. Bryce2, Rauzah Hashim1
1

Department of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia


2

Pharmacy School, University of Manchester, Manchester, M13 9PT, UK

Full atomistic molecular dynamics simulation method is used to study the hydrated
bilayers modelled by single and branched chain glycolipids, namely MalC 12 (12%wat),
Mal-C 12 (23%wat),
Mal-C 12 C 8 (R)(25%wat),
MalC 12 C 8 (S)(25%wat), and Mal-C 12 C 8 (RS)(25%wat), in liquid crystalline L phase, in
order to understand their structural and dynamical behaviours subjected to the
variation in temperature, water concentration, chain branching, and chiral isomerism.
The results show that the incremental of hydration level correspondingly increases the
area per lipid due to the penetration of water molecules into the sugar headgroups.
But the single chain glycosides, Mal-C 12 (12%wat) and Mal-C 12 (23%wat), show a
different trend in the area per lipid values. The bimodal distribution of angle between
the chains of lipid with the z-axis for Mal-C 12 (23%wat) shows that the chain tend to
orient near to the headgroup region and its angular distribution of the sugar rings from
the headgroup possibly indicate that the non-reducing sugar ring flip and protrude
into the headgroup region. Looking the behaviour of chain and headgroup, we suggest
the Mal-C 12 (23%wat) system may be begin to shift into a metastable phase where,
the lipids may try to reorient themselves into different assembly structure.
Additionally, our simulation show that the intermolecular hydrogen bonding (HB) for
all the oxygen sites of both the sugar rings in maltose headgroup do not change much
although the bilayers are under the effect of water concentration and temperature. But
the water-lipid HB is dependent to the hydration concentration where, when the
hydration level increases, the water-lipid HB increases too. We found the nonreducing sugars from all bilayer systems rotates faster than the reducing sugar,
because the reducing sugar placed in between the alkyl chain and the non-reducing
sugar which has been hydrated with water. Nonetheless, the presence of
intermolecular HB helps to increase the sugar rings' rotational diffusion. Finally we
found the exocyclic groups from all glycosides rotate much quicker than the sugar
ring itself and there is no chirality effect to the rotational diffusion. Meanwhile, the
order parameter is quite sensitive to the temperature and water concentration and
there is a subtle effect of chirality on the bond order parameter of lipids, especially in
the racemic mixture of bilayer.

Contact: vjramana@gmail.com

127

Laying the Foundations of a Non-Linear Adaptive Force


Matching Algorithm: An Economic, Systematic, & ab initio
DerivedRe-Parameterization of a Simple Water Model
I-Shou Huang, Ming-Kang Tsai*
Department of Chemistry, National Taiwan Normal University, Taipei 10677, Taiwan
Empirical potential molecular dynamic(MD) simulation is the most economic
tool we have for large scale samplingas the scope of our interested system increases,
using ab initio potential energy surface rapidly becomes cost prohibitive. However,
the accuracy of empirical MD depends greatly upon its force field, and the making
thereof has traditionally been more of an arcane art rather than a modern science. As a
response to this, a recent methodology of force field generation has started to gain
grounds, known as Force Matching. The method uses forces calculated from ab initio
methods to fabricate a force field, thereby reproducing the high level theory results of
quantum mechanics. Further developments in this methodology has greatly increased
its robustness and cost efficiency. One notable improvement is Adaptive Force
Matching (AFM)[1], which cut cost in referential ab initio calculations by reducing its
size and theory level, but introduces sampling, weighing and iterative processes to
make up for the loss of efficacy. Ultimately AFM drastically reduces cost by moving
towards linear scaling. Despite that, recent AFM experiments have been limited to
parametrically linear force fields, which have heavily restricted applications.
Therefore, the present work attempts to extend the subject to non-linear potentials by
re-parameterizing a simple point charge water model, which is nonlinear, via an in
house-developed AFM algorithm.

[1] Akin-Ojo O., Song Y., Wang F., J. Chem. Phys. 129, 064 108 (2008)
Contact: mktsai@ntnu.edu.tw

128

High Speed Molecular Dynamics Simulations in Designing


Ankyrin that Interact with E protein of Dengue Virus II
Wei Lim Chong,1 Sharifuddin Md Zain1, Noorsaadah Abdul Rahman1, Rozana
Othman1, Shatrah Othman1 and Vannajan Sanghiran Lee1
1

Drug Design and Development Research Group, University of Malaya 50603


Lembah Pantai, Kuala Lumpur Malaysia

Implementation of Graphical Processor Units (GPU) has accelerated the molecular


dynamics simulation compared to existing CPU system and is therefore employed to
search for the protein inhibitors in targeting the dengue proteins. Domain III of the E
protein has been targeted as it mediates the fusion between dengue virus (DENV) and
host cell membrane [1]. A number of reports recently have proposed ankyrin
molecules to substitute for antibody [2,3] as they offer several advantages over
antibody. Hence, potential ankyrin repeat protein that can recognise E protein of
DENV has been proposed and further designed from accelerated molecular dynamics
simulations using PMEMD.CUDA under AMBER12 on GPU-enabled workstation.
Ankyrin residues that interact with domain III within 5 are identified and those
observed to have a positive interaction energy have been replaced by other amino acid.
Binding affinity is enhanced when aspartic acid is replaced by glutamic acid at
residue 34 on ankyrin and resulted binding energy improved from -24.11 kcal/mol to
-42.38 kcal/mol during 6-10 ns. A tighter binding mode between the designed ankyrin
and domain III (wild-type) has been observed from root mean square fluctuation
(RMSF) analysis. Besides, designed ankyrin is capable to bind better with mutated
domain III (K307A) than reported antibody.
References:
[1]. S. L. Allison, J. Schalich, K. Stiasny, C. W. Mandl, C. Kunz and F. X. Heinz, J
Virol., 69, 2 (1995).
[2]. H. K. Binz, M. T. Stumpp, P. Forrer, P. Amstutz and A. Pluckthun, J Mol Biol 332,
(2003).
[3]. A. Schweizer, P. Rusert, L. Berlinger, C. R. Ruprecht, A. Mann et al., PLoS Pathog 4, 7
(2008).

Contact: vannajan@gmail.com and wlchongwilliam@gmail.com

129

GPU accelerated Molecular Dynamics Simulations in the


Designing of Ankyrin as specific binders of ERK2
Vertika Gautam1 , Sharifuddin Md Zain1, Noorsaadah Abdul Rahman1 and Vannajan
Sanghiran Lee1
1

Drug Design and Development Research Group, University of Malaya 50603 Lembah
Pantai, Kuala Lumpur Malaysia

Various posttranslational modifications (PTMs) of proteins play a pivotal role in signal


propagation and regulate the function of numerous proteins in signaling networks.
Extracellular signal-regulated kinase 2 (ERK2), undergoes phosphorylation to regulate
several physiological and pathological phenomena, including cancer [1]. Hence, inhibition of
overexpressed kinases is much required to control the diseased condition. Owing to their
improved stability and better binding, DARPins are replacing the conventional monoclonal
antibodies in the study of PTMs [2].
In the present work, crystal structure of DARPins (from synthetic library) in complex with
ERK2 [3], were studied for their interaction (PDB ID 3ZUV), from accelerated molecular
dynamics simulations using PMEMD.CUDA under AMBER12 on GPU-enabled workstation.
Good binding is suggested during 6-10ns with an energy of -52.21 kcal/mol and decomposed
energy data suggested the key residues (Arg-189, pTyr-185, Glu-184, Tyr-231, Lys-230,
Lys257) of kinase involved in the binding with the DARPins. This knowledge can be further
used in the designing of Ankyrin which can be potential specific binder for the
phosphorylated ERK2.
References:
[1]. J. Seo , K.J. Lee, Biochem Mol Biol 37, 35 (2004)
[2]. H.K. Binz, P. Amstutz , A. Plckthun, Nat Biotechnol 22, 575 (2004).
[3]. L. Kummera, P. Parizeka, P. Rubeb, B. Millgrammb, A. Prinzb, R. E. Mittla, M. Kaufholzc,
B. Zimmermannc, F. W. Herbergb, and A. Plckthuna, PNAS E2248, (2012).

Contact: vannajan@gmail.com and vartikapisces@gmail.com

130

Searching for GSK3b Kinase Inhibitros: Molecular Docking,


Molecular dynamics Simulation, and Kinase Assay
Chia-Jen Hsu() 1, Chia-Ming Chang() 1, Wen-Chi Hsu() 1,
An-Lun Liu() 1, Guan-Chiun Lee() 2, *, Ying-Chieh Sun() 1,*
1

Department of Chemistry, National Taiwan Noramal University, Taipei, Taiwan


Department of Life Science, National Taiwan Normal University, Taipe, Taiwan

Glycogen synthase kinase-3 GSK-3 is an important protein target for


treatment of several diseases. When the activity of GSK-3 is too high, it overphosphorylates downstream proteins and causes some diseases such as cancer,
inflammation, and Alzheimers Diseases. This study utilized molecular docking,
molecular dynamics simulation, and kinase assay to search new GSK-3 kinase
inhibitors.
We used molecular docking method to do high throughput virtual screening in the
ZINC Database and the Enamine Database to find out some potential small molecular
compounds, and suggested these compounds for kinase assay. Among the 27
compound undergone kinase assay, 12 compounds were identified to be active, and
were recommended for further cell and animal assays. Thermodynamic integration
MD simulation was also employed to aid in further inhibitor design.
The thermodynamic integration molecular dynamics simulation reproduced the
relative protein-ligand binding free energy of a pair of analogous GSK3 kinase
inhibitors of available experimental data well. The computation for the pair gave a
G of 1.0 kcal/mol, which was in reasonably good agreement with the experimental
value of -0.1 kcal/mol, and the error bar was estimated to be 0.5 kcal/mol. The
protocol was then applied to predict the affinity for other analogs as well as binding
modes. The computed results will be reported and discussed.

[1] Lee, H.C.; Hsu, W.C.; Liu, A.L.; Hsu, C.J.; Sun, Y.C., J. Mol. Graphics & Model.
2014, 51, 37-49.

Contact: Ying-Chieh Sun, sun@ntnu.edu.tw; Guan-Chiun Lee, gclee@ntnu.edu.tw

131

Characterization of Shape Resonances on Trimethyl


Phosphite, Trimethyl Phosphate,
and Phosphoryl Chloride
Yin-Cheng Chen (), Yu-Jui Su () and Hsiu-Yao Cheng ()
Department of Chemistry, Tunghai University, Taichung, 407 Taiwan, R. O. C.

The Metastable anions of phosphate groups play important roles in the breaking of
DNA strands. The stabilized Koopmans theorem in long-range corrected density
functional theory is used to investigate the shape resonances of trimethyl phosphite,
trimethyl phosphate, and phosphoryl chloride. In this approach, stabilization is
accomplished by systematically scaling the most diffuse functions in the basis set.
The resonance energies are then identified by investigating the relationship between
the resultant eigenvalues and scale parameter. The detailed characteristics of
resonance orbitals are also analyzed. Results indicate the presence of several lowlying * and * shape resonances. Several shape resonances with strong d
characters have also been identified. These results will help us understand the
bonding and electron transfer in the breaking of DNA strands. [1], [2]

[1] P.D. Burrow, G.A. Gallup, and A. Modelli, J. Phys. Chem. A 112, 4106 (2008).
[2] H.-Y. Cheng and C. W. Chen, J. Phys. Chem. A. 115, 10113 (2011).

Contact: hycheng@thu.edu.tw

132

First Principles Calculations of Elastic Parameters of


Perovskite Oxides
Narasak Pandech1,2, Kanoknan Sarasamak3, Sukit Limpijumnong1,2
School of Physics and NANOTEC-SUT Center of Excellence on Advanced
Functional Nanomaterials, Suranaree University of Technology,
Nakhon Ratchasima 30000, Thailand
2
Thailand Center of Excellence in Physics (ThEP Center), Commission on Higher
Education, Bangkok 10400, Thailand
3
College of Nanotechnology, King Mongkut's Institute of Technology Ladkrabang,
Bangkok 10520, Thailand
1

The mechanical properties, i.e., hardness, Poisson's ratio (transverse expansion in


response to the compression), and shear strength, of perovskite oxides depend on both
metal oxide lattices that are intercalated. By tuning metal on the A-site and B-site,
specific control of each mechanical property can be achieved. In this work, the
elastic constants of series of perovskite oxides were studied by first principles
approach.[1] Both A-site and B-site cations were systematically varied in order to see
their effects on the elastic parameters. To study the effects of A-site cations, we
studied the elastic properties of perovskite ATiO 3 (A = Be, Mg, Ca, Sr, or Ba). For Bsite cations, we studied the elastic properties of PbBO 3 (B = Ti, Zr, or Hf). The
density functional first principles calculations with local density approximation (LDA)
and generalized gradient approximation (GGA) were employed. It is found that the
maximum C 11 elastic constant is achieved when the atomic size of the cations at Asite and B-site are comparable. We also found that C 12 elastic constant is sensitive to
B-site cations while C 44 elastic constant is more sensitive to A-site cations. Details
and explanations for such dependencies are discussed. Example of the detailed
calculations of elastic parameters will be illustrated.

Illustration of the ideal cubic


perovskite crystal: (a) the six-atom
oxygen cage surrounding
the B cation, (b) the twelve-atom
oxygen cage surrounding the A
cation, and (c) both types of
oxygen cages. The large green
spheres represent A cations,
medium-size yellow spheres
are B cation, and small red spheres
are oxygen anions. [1]

[1] N. Pandech, K. Sarasamak, and S. Limpijumnong, J. Appl. Phys. 117, 174108


(2015)
Contact: sukit@sut.ac.th

133

A Computational Study of CoH/CoMe Bond Dissociation


in the [(por)CoIIIL] System (L = H/Me)
Gou-Tao Huang* and Jen-Shiang K. Yu
Department of Biological Science and Technology, and Institute of Bioinformatics
and Systems Biology, National Chiao Tung University, Hsinchu 30013, Taiwan
CoH/CoMe bond dissociation is an important step in radical polymerization

catalyzed by the [(por)CoII] system. The homolytic bond dissociation is studied


using density functional theory and multi-configuration CASSCF/CASPT2 methods.1
The CASPT2 level based on CASSCF with 10 electrons in 12 active orbitals predicts
the CoH bond dissociation energy at 47.3 kcal mol1, in agreement with
experimental values between 47 and 53 kcal mol1.2 Benchmark calculations are
performed with a series of pure and hybrid density functionals, including BP86,
B3P86, BLYP, B3LYP, PBE, PBE0, M05, M06L, and M06. CoMe bond
dissociation analysis is also reported. Two reactions in terms of the hydrogen
abstraction of [(por)CoIIIH] by vinyl acetate and methacrylonitrile, followed by the
carbon-cobalt bond homolysis of CoC(CH 3 ) 2 CN and CoCH(CH 3 )OAc, are
investigated.

O
H
O
vinyl acetate
III
(por)Co H +

H-abstraction

H
H
O

III
(por)Co

CN

III
(por)Co

H
CN

methacrylonitrile
Co C bond dissociation
O
H
II
(por)Co

H H
CN
H
H H

[1] K. Andersson, P. A. Malmqvist, B. O. Roos, A. J. Sadlej, and K. Wolinski, J.


Phys. Chem. 94, 5483 (1990)
[2] D. C. Woska, Z. D. Xie, A. A. Gridnev, S. D. Ittel, M. Fryd, and B. B.
Wayland, J. Am. Chem. Soc. 118, 9102 (1996)
Contact: gth@nctu.edu.tw

134

Density Functional Theory Calculation on the Dissociation


Mechanism of Nitric Oxide Catalyzed by Cu 4 cluster in
ZSM-5 (Cu 4 -ZSM-5) and Bimetal Cu 3 Fe in ZSM-5
(Cu 3 Fe-ZSM-5)
Chen-Hao Yeh1 and Jia-Jen Ho1
1

Department of Chemistry, National Taiwan Normal University, Taipei, Taiwan

Zeolite-based catalysts have been investigated as a well-known catalyst in a


selectively catalytic reduction (SCR), in the conversion of NO to N 2 molecule [1], [2].
Here we have performed periodic DFT calculations to simulate pure metal, Cu 4 , and
bimetal Cu 3 Fe clusters, on the ZSM-5 by introducing a single Al atom in the unit cell
of ZSM-5 (Si/Al ratio = 95). The calculated results show that the most stable
structures of both Cu 4 and Cu 3 Fe clusters in ZSM-5 are both T d configuration. In
addition, the NO bond length would be elongated from 1.15 to 1.25 ~ 1.30 in
the adsorption of NO on metal-cluster stabilized zeolites (both Cu 4 -ZSM-5 and
Cu 3 Fe-ZSM-5), being longer than the counterparts on single-metal anchored zeolites.
Furthermore, the calculated NO bond cleavage barrier on Cu 3 Fe-ZSM-5 was lower
than its counterparts on Cu 4 -ZSM-5. To understand the electronic properties, we
performed the calculation of Bader charge analysis and local densities of states, and
the result was explicable.
[1] T. Zhang, J. Liu, D. Wang, Z. Zhao, Y. Wei, K. Cheng, G. Jiang, A. Duan, Appl.
Catal. B, 148-149, 520 (2014).
[2] G. Moretti, C. Dossi, A. Fusi, S. Recchia, R. Psaro, Appl. Catal. B, 20, 67 (1999).

Email: mrprofya@gmail.com

135

First-Principles Study of Alkali Metal Intercalated in


Transition Metal Dichalcogenides
Thanundon Kongnok,1 Sirichok Jungthawan,1, 2 and Sukit Limpijumnong1, 2
1

School of Physics and NANOTEC-SUT Center of Excellence on Advanced


Functional Nanomaterials, Suranaree University of Technology, Nakhon Ratchasima
30000, Thailand
2
Thailand Center of Excellence in Physics (ThEP), Commission on Higher
Education, Bangkok 10400, Thailand

Transition Metal Dichalcogenides (TMDC) materials are semiconductors having


layered structure, such as MoS 2 , MoSe 2 , MoTe 2 , WS 2 , WSe 2 and WTe 2 . In these
layered structure, TMDCs monolayers are bounded weakly by the Van der Waals
interaction. In the bulk form, these TMDCs have an indirect band gap where valence
band maximum and conduction band minimum are located at the point and near the
middle point between -K point, respectively. However, the band gap of a monolayer
TMDC is direct and is located at the K point. The electronic characteristic of the
monolayer can be restored in the layered structure TMDCs by intercalating alkali
metal such as Li, Na, K, and Rb in the interlayer gap [1]. The expansion of the
interlayer gap is large enough to reduce the electronic interaction between the
monolayers; creating a quasi-monolayer character. In this work, the effects of the
intercalation are investigated by using first-principles calculations. The results show
that the band gap is increased and changes from indirect to direct; caused by the
expansion of the interlayer spacing between layers and the contribution of electrons
from alkali metal to the conduction band. The contributed electrons from the
intercalated metal into the conduction band are delocalized in the layer that slightly
increases the lattice constant. Our results suggested that the different atomic size of
intercalated alkali metals provides an opportunity to tune the interlayer spacing, hence,
electronic characteristics for broad applications in nanoelectronics and
optoelectronics.
[1] T. Eknapakul, P. D. C. King, M. Asakawa, P. Buaphet, R.-H. He, S.-K. Mo, H.
Takagi, K. M. Shen, F. Baumberger, T. Sasagawa, S. Jungthawan, and W.
Meevasana, Nano Lett. 14, 1312 (2014).

Contact: Thanundon_kongnok@hotmail.com

136

First Principles Study of the Doping Effect on Graphene


from the Sn impurities in the SiO 2 Substrates
An Ho, Kun-Han Lin, and Yu-Yun Huang, Chin-Lung Kuo*
Department of Materials Science and Engineering, National Taiwan University,
Taipei, Taiwan

Graphene is a promising candidate for the novel carbon-based nanoelectronic devices


primarily due to its extremely high carrier mobility of a few hundred thousand cm2 V1 -1
s at room temperature. For device fabrication, however, graphene usually needs to
be placed on top of an insulating substrate and the interactions between graphene and
the underlying substrate can substantially downgrade the carrier mobility of the
adsorbed graphene layer, which may eventually limit its performances. Therefore, it
is of great importance to develop a detailed understanding regarding the electronic
structure changes of graphene via dopants and the associated induced-Si defects in the
underlying SiO 2 substrates to control or further improve its performance. In this
presentation, we will briefly introduce our recent study on the effects of the tin-doped
SiO 2 substrate on the electronic structure changes of graphene monolayer. Unlike
other conventional dopants (boron or phosphorus atoms, etc.), tin atoms can
substitutionally replace Si atoms in SiO 2 or form metallic tin clusters or tin oxides on
top of the substrate after high-temperature annealing. Accordingly, we have
performed our calculations by placing graphene monolayer on pure tin metal (-Sn),
tin oxides (rutile SnO 2 ) and Sn-doped SiO 2 substrates, respectively. Our calculated
results showed that the work function of -Sn is around 0.16~0.19 eV smaller than
that of graphene monolayer, which indicates that -Sn clusters in the SiO 2 substrate
are possible to induce n-type doping effect on graphene. Furthermore, when graphene
was placed on a rutile SnO 2 substrate, our calculations revealed a remarkable p-type
doping effect on graphene from the substrate, which was mainly attributed to the
charge transfer from graphene to the fivefold coordinated Sn atoms on the SnO 2
surface. Nevertheless, such a p-type doping effect on graphene was found to be
significantly reduced when the O vacancies are present on the SnO 2 surface. On the
other hand, we have also identified several possible configurations of the
substitutional Sn atoms in the SiO 2 bond network. Their atomic bonding structures
and the associated effect on the electronic structure change of monolayer graphene
will be discussed accordingly in this presentation.

Contact: chinlung@ntu.edu.tw

137

Alkaline earth metal halides: New candidate 2D materials


Duc-Long Nguyen,1 Shi-Hsin Lin,2 and Jer-Lai Kuo2
1

Molecular Science and Technology Program, TIGP


Institute of Atomic and Molecular Sciences, Academia Sinica
Department of Physics, National Central University
Institute of Atomic and Molecular Sciences, Academia Sinica.

Research on 2D materials has grown rapidly over the past several years after the
enormous successful of Graphene. The ongoing project in searching for new 2D
materials near the ionic instability(3D structures are favored), with Graphene placing
at the first spectrum of covalent bonded system, is presented. By applying density
functional theory, we investigated the monolayer 1H polytype alkaline earth halides.
In this study, we focused on the new candidate for 2D materials, their 1H structural
properties, band structures using LDA and PBE functional compared with the
reported 1T structure [1]. We found that monolayer 1H alkaline earth metal halides
possess electronic structure ranging from insulator to semiconductor with the indirect
bandgap of around a few eV.

[1] Shi-Hsin Lin and Jer-Lai Kuo, Phys. Chem. Chem. Phys., 2014, 16, 20763.
Contact: Longnguyenqtr@gmail.com

138

Theoretical Study of Gas Diffusion Through Porous


Graphene Under Pressure
Yuwadee Suwan, Sirichok Jungthawan, and Sukit Limpijumnong
1

School of Physics, Institute of Science, Suranaree University of Technology, Nakhon


Ratchasima 30000, Thailand
2
NANOTEC-SUT Center of Excellence on Advanced Functional Nanomaterials,
Suranaree University of Technology, Nakhon Ratchasima 30000, Thailand
3
Thailand Center of Excellence in Physics (ThEP), Commission on Higher Education,
Bangkok 10400, Thailand

The gas separation properties of porous graphene (PG) membrane on SiO 2 substrate
for simple molecules (H 2 , O 2 , and CO 2 ) under pressure have been investigated by
using the first-principles density functional theory. The van der Waals interaction
was taken into account by using Grimmes force field (PBE-D2) approach [1]. The
deformation of the membrane is described by Henckys solution [2] for the clamped
circular membrane subjected to a pressure difference across the membrane. It was
found that the diffusion barrier decreases with increasing pressure for H 2 , O 2 and
CO 2 . The pressure difference across the membrane can effectively increase the
diffusion rate of the studied molecules, H 2 , O 2 , and CO 2 by up to 4, 8, and 12 orders
of magnitude, respectively (in the pressure range of 0-5 MPa). The selectivity or
relative diffusion rate of PG for the diffusion of H 2 , O 2 , and CO 2 molecules at p =
5 MPa relative to the CO 2 diffusion rate at p = 0 MPa are 1024, 1019, and 1012,
respectively. The results suggest controllable gas separation properties of PG by
applying a pressure different across the membrane.

[1] S. Grimme, J. Comp. Chem. 27, 1787 (2006).


[2] W. B. Fichter, NASA Technical Paper, 3658 (1997).

Contact: y.suwan09@gmail.com

139

Particle size effects of sulfonated graphene supported Pt


nanoparticles on ethanol electrooxidation: combined
experiment and DFT study
Hung-Lung Chou,1,* Chia-Liang Sun,2,* Jui-Shiang Tang,2 Nicolas Brazeau,3
Jhing-Jhou Wu, 2 Spyridon Ntais, 2 Chung-Wei Yin, 2 Elena A. Baranova,3 Yi-En
Liu,1 Ming-Han Tsou,1 Hong-Ming Chen,1
1

Graduate Institute of Applied Science and Technology, National Taiwan


University of Science and Technology,Taipei 106, R.O.C
2
Department of Chemical and Materials Engineering, Chang Gung University,
Kwei-Shan, Tao-Yuan 333, Taiwan
3
Department of Chemical and Biological Engineering, University of Ottawa, 161
Louis-Pasteur St., Ottawa, ON K1 N 6N5, Canada
Fuel cells are promising alternative in automobile and stationary power generation.
Direct ethanol fuel cells(DEFCs) ofer significant advantages due to the non-toxicity
and renewability ethanol as well as its high power density. Development of the
efficient catalysts for ethanol oxidation reaction (EOR) has attracted great attention
and represents one of the major challenges in electrocatalysts. Graphene, one-atom
thick nanocarbon materials, has attracted much attention recently in a variety of
applications. The sulfonation of graphene is able to make it hydrophilic, which
enhances its dispersibility in aqueous solvents. Furthermore, sulfonated increases the
adsorption and uniform distribution of the Pt nanoparticles, which increases both the
electrocatalytic activity and the durability. In this study, theoretical calculations
demonstrated that the sulfonate functional group can donate charge to Pt, enhanced
the adsorption energy of Pt, and then reduce the adsorption energy of CO on Pt. Then
experimentally five kinds/sulfonated-graphene (Pt/sG) catalysts were synthesized via
the control of pH values during the preparation of five-selected colloidal
nanoparticles. Among all catalysts, Pt-sG (2.5 nm) has the highest peak current
density in EOR. [1]

[1] Chia-Liang Sun, Jui-Shiang Tang, Nicolas Brazeau, Jhing-Jhou Wu, Spyridon
Ntais, Chung-Wei Yin, Hung-Lung Chou, Elena A. Baranova, Electrochimica Acta,
in-press (2015).
Corresponding author: HLCHOU@mail.ntust.edu.tw
Contact: B10330205@mail.ntust.edu.tw
Acknowledgement:
We thank the NCHC and NTUST for providing massive computing time. Financial
support from the National Science Council under Contracts No. NSC 102-2221-E011-025 and MOST 103-2221-E-011-041 are also gratefully acknowledged.

140

Magnetic Property of Fullerene C 20 : A First-Principles Study


Icuk Setiyawati1and Yu-HuiTang1*()
1

Department of Physics, National Central University, Jhong-Li, Taiwan

From the production in the gas phase by Prinzbach[1], the C 20 as the smallest fullerene has
been attracted considerable attention among scientists. In the following year, Wang et
al[2]sucessfully synthesized the solid phase of C 20 using ion beam irradiation method and
found that the fullerene C 20 behave as the building block of hexagonal crystal. In addition, Jo
et al. [3] predicted the magnetism in C 20 cage structure due to its pentagon-bunching
structure.
To investigate the underlying mechanism of the magnetism of fullerene C 20 cage structure,
we employed the density functional theory (DFT) within thenonequilibrium Keldysh Greens
function (NEGF) formalism to study the spin-polarized density of states of the isolated
nonmagnetic C 60 and C 20 bowl-like molecules, which are truncated by the mixture of
pentagons and hexagons as shown in Figs. 1(a) and (b), and of the isolated magnetic C 20 cage
and C 15 bowl-like molecules, which exhibit purely pentagon-bunching structure as shown in
Figs. 1(c) and (d). For the C 15 bowl-like structures, the spin-polarized molecular levels are
mainly contributed by those C atoms on the zigzag edge, while, for the C 20 cage structure,
all molecular levels are spin-polarized resulting from the ziazag boundaries between
pentagons. Such zigzag-boundary induced magnetic properties of C 20 cage and C 15 bowl-like
molecule can be analog to the graphene nanoribbon with zigzag edges [4]. Moreover, the
non-magnetic and insulating properties of C 60 and C 20 bowl-like molecules can be attributed
to the mixture of zigzag and armchair boundaries between hexagon and pentagons.(Contract
No. NSC 102-2112-M-008-004-MY3)

(a)

(b)

(c)

(d)

[1] H. Prinzbach et al., Nature (London) 407, 60 (2000).


[2] Z. Wang et al., Phys. Rev. Lett A 280, 351-356 (2001).
[3] C. Jo and J. I. Lee, Journal of the Korean Physical Society 47, 646-649 (2005).
[4] K. Nakada et al., Phys. Rev. B 54,17954-17961 (1996).
Contact: yhtang@cc.ncu.edu.tw

141

Stability study of ring-like sheet of Ag atoms wrapping CNT


Hagita K,1 Ono Y,2 and Tejima S2
1

Department of Applied Physics, National Defense Academy, Yokosuka, JAPAN


Research Organization of Information Science and Technology, Tokyo, JAPAN

Composite of Carbon nano-tube (CNT) and metallic atoms have received much
attention in academia and industry. For example, it is reported that composites of
CNT and Cu atoms shows high current capacity [1]. We surveyed behavior of a few
ten metallic atoms (ex. Ag, Cu, Zn) around CNT with plane-wave DFT simulations
using Quantum Espresso (PWscf) [2]. In our DFT structural relaxation starting from
randomly placed Ag atoms around CNT, sheet like structures are often observed. On
the other hand, for the cases of Cu, sheet-like structure is not observed although
aggregates are observed. Thus, we emerged a (first) hypothesis that ring-like sheet of
Ag atoms with wrapping CNT (shown in Figure 1) becomes stable or meta-stable. As
second hypothesis, we expected that larger ring-like sheet of Ag atoms is more stable.
To confirm these hypotheses, we studied stabilities of various Ag sheets wrapping
CNT. We estimated total energies of these Ag sheets and a cluster (a 3d aggregate) of
Ag atoms which is not wrapping CNT but placed beside CNT.
As the first test, we performed structural relaxation starting from a single ring of
Ag atoms wrapping (5,5)-CNT of 100 Carbons under the periodic boundary
conditions. After structural relaxation, only cases of 14, 15 and 16 Ag atoms keep
ring structure. Total energy is larger than that of aggregates of Ag atoms. For 14 Ag,
the difference is 0.66 Ry (=-2167.679Ry+2168.336Ry) and not negligible small. For
1 pico-sec DFT-MD simulations under 200 K, it seems to be keeping ring structure.
In this paper, we made simulation models using rings or a spiral of Ag atoms as
shown Figure 3. There are two types of bond orientations which depend on spacing of
neighboring rings or a spiral as shown in Figure 4. For example sheets of 45 Ag
atoms can be made of 5 rings of 9 Ag with bonds like Fig 4 (above) or 3 rings of 15
Ag with Fig 4 (below). We examined various cases of various number of Ag atoms.
As result, total energy of a 3d aggregate besides CNT seems to be always smaller
than that of sheet-like structures of Ag atoms wrapping CNT. Here, the difference is
about 1 Ry for 45 Ag atoms. Moreover, both cases of 45 Ag atoms cannot keep ringlike sheet structure by 1 pico-sec DFT-MD with 50K. It means that ring-like sheet
structure wrapping CNT is unstable than a single ring. Thus, for the first hypothesis,
we concluded a ring of Ag atoms is meta-stable. We refuted the second hypothesis.

Figure 1 Snapshot of Ag
sheet wrapping CNT

Figure 2 A single Figure 3 Ring-like


ring of Ag atoms sheets made of
rings and a spiral
wraping CNT

Figure 4 Two types


of bond orientation
of Ag sheet

[1] C. Subramaniam, et. al., Nature Communications 4 (2013) Article #: 2202.


[2] P. Giannozzi, et. al., J. Phys.:Condens. Matter 21, 395502 (2009).
Contact: hagita@nda.ac.jp
(HPCI project ID: hp140194)

142

Density Function Theory Used to Investigate the


Adsorption and Charge Transfer in the Tri-iodine-Pt(111)
Slab Surfaces Interaction
Hung-Lung Chou,a,* Rick John, b P. L. Lu, c Y. H. Tseng, d W. C. Chene
a

Graduate Institute of Applied Science and Technology, National Taiwan


University of Science and Technology,Taipei 106, R.O.C
b
Nanoelectrochemistry Laboratory, Department of Chemical Engineering,
National Taiwan University of Science and Technology, Taipei 106, Taiwan
c
Department of Materials Science and Engineering, National Taiwan University of
Science and Technology, Taipei 10617, Taiwan
d
Inter-disciplinary Bachelors program, National Taiwan University of Science
and Technology, Taipei 106, Taiwan
e
Jin-Ying Bachelors program, National Taiwan University of Science and
Technology, Taipei 106, Taiwan
Density functional theory calculations for the adsorption and charge transfer energies
of tri-iodine on the Pt(111) surface are presented. In this work, the calculated
adsorption and structural energies, together with the deduced charge transfer
mechanism and the resulting electronic structures of I3 -Pt(111) systems are shown to
be in good agreement with experimentally derived information. The adsorption
energies for iodine atom on the fcc, hcp, bridge, and atop sites of the Pt(111) surface
were determined using an ab initio DFT method. A Pt(111) slab model was used,
from which the charge transfer energy was determined by Bader charge analysis. The
results show that the plane-wave DFT approach correctly describes the adsorption of
iodine on the Pt(111) surface and supports the use of Bader charge analysis in
resolving surface science problems related to DSSC.

Corresponding e-mail: HLCHOU@mail.ntust.edu.tw


Contact: B10232030@mail.ntust.edu.tw
Acknowledgement:
We thank the NCHC for providing massive computing time. Financial support from
the National Science Council under Contracts No. NSC 102-2221-E-011-025 and
MOST 103-2221-E-011-041 are also gratefully acknowledged.

143

Ethylene Carbonate Adsorption and Decomposition on


Li x Mn 2 O 4 Cathode: A DFT study
Kai-Hao Tsau, Yu-Tsung Liu and Jyh-Chiang Jiang
Department of Chemical Engineering, National Taiwan University of Science and
Technology, Taipei, 106, Taiwan, R.O.C
The development of electrochemical energy storage technologies, such as lithium-ion
batteries (LIBs), will play a grand role in the advancement of alternative renewable
energy sources. The adsorption and decomposition mechanism of electrolyte on the
cathode surface of LIBs is one of the governing factors which control the stability,
capacity, and cyclic life. In this work, first principles calculations are used to study
the adsorption and decomposition reaction mechanisms of ethylene carbonate (EC) on
the (100) surface of fully discharged LiMn 2 O 4 , and the half-charged Li 0.6 Mn 2 O 4 [1],
[2]. The adsorption strength and electronic properties of various configurations are
discussed by using density of states (DOS), projected density of states (PDOS) and
electron density difference (EDD). Moreover, the initial decomposition mechanisms
of EC on the surfaces is investigated by examining the minimum energy path between
two minima using the climbing image nudged elastic band reaction-pathway sampling
scheme. Even though adsorption and decomposition reaction can occur on the
surfaces, for all configurations studied, the results show that the decomposition of EC
is more likely on the charged surface despite having higher adsorption energy on the
fully discharged surface. In general, this work aims to give an insight into the initial
stages of surface catalyzed electrolyte decomposition reactions on spinel cathode
structure.
[1] Joho, F.; Novk, P. Electrochim. Acta, Phys. 45, 3589 (2000)
[2] K. Leung J. Phys. Chem. C 116 18 9852 (2012)
Contact: jcjiang@mail.ntust.edu.tw

144

Density Function Theory Used to Investigate the Adsorption


and Dissociation of O 2 on Fe x Pt 1-x (111) and Pt(111) and
Fe(100) Slab Surfaces
Hung-Lung Chou,a,* Rick John, b P. L. Lu, c Y. H. Tseng, c Y. Lee, c C. L. O, d W.
C. Chen, e W. J. Lin, e N. T. Chiang, e Y. C. Li, e Y. H. Huang, d H. H. Tsai, e L. Y.
Huang, d Y. R. Chen, e Y. S. Lind
a

Graduate Institute of Applied Science and Technology, National Taiwan


University of Science and Technology,Taipei 106, R.O.C
b
Nanoelectrochemistry Laboratory, Department of Chemical Engineering,
National Taiwan University of Science and Technology, Taipei 106, Taiwan
c
Department of Materials Science and Engineering, National Taiwan University of
Science and Technology, Taipei 10617, Taiwan
d
Inter-disciplinary Bachelors program, National Taiwan University of Science
and Technology, Taipei 106, Taiwan
e
Jin-Ying Bachelors program, National Taiwan University of Science and
Technology, Taipei 106, Taiwan
Density functional theory calculations have been performed to study the adsorption of
O adatom and O 2 molecule and the dissociation of O 2 molecule on the (111) facets of
ordered Pt and PtFe alloy. Results are compared with those obtained on two Pt(111)
surfaces, one at the equilibrium lattice constant and the other laterally compressed by
2% to match the strain of lattice constant in the Pt alloys. The magnitudes of the
adsorption energies of O 2 follow in the systems: compressed Pt(111) < Pt(111) <
PtFe(111). The reduced activity of the compressed Pt(111) and Pt skins for oxygen
molecule can be rationalized as being due to the shifting of the d-band center
increasing away from the Fermi level. We propose that an alleviation of poisoning by
O and enhanced rates for reactions involving O may be some of the reasons why Pt
skins are more active for the oxygen reduction reaction (ORR) in fuel cells. The
theoretical model here paved the way toward the large-scale computational screening
for both active and economic electrode, pointing to a simple way to screen for
improved cathode catalysts in future.

Contact: hlchou72@gmail.com
Acknowledgement:
We thank the NCHC for providing massive computing time. Financial support from
the National Science Council under Contracts No. NSC 102-2221-E-011-025 and
MOST 103-2221-E-011-041 are also gratefully acknowledged.

145

Formaldehyde Decomposition on Boron Doped Graphene


Decorated with Transition Metal Atoms A First Principles
Study
Yi-Pin Lin, Jyh-Chiang Jiang*
Department of Chemical Engineering, National Taiwan University of Science and
Technology, Taipei, Taiwan,

Nowadays controlling indoor air quality is attracting immense research attention


since humans are spending more time in the indoor activities. Formaldehyde (HCHO)
is the most common highly toxic volatile carcinogen, which is found in many
households and offices.[1] The International Agency for Research on Cancer (IARC)
concluded in 2009 that longtime exposure to HCHO causes nasal tumors,
nasopharyngeal cancer and leukaemia. Etc. [2] In order to clean the indoor air, many
strategies have been proposed to remove HCHO. However, catalytic oxidative
decomposition of HCHO is considered the most promising approach for removal of
indoor HCHO, because of its environmental friendliness.
In this work, with the aid of density functional (DFT) calculations, we have
investigated the possible decomposition pathways of HCHO on metal clusters (V, Co,
Ni) supported boron-doped graphene. The results show that, the dehydrogenation
reactions of HCHO on the metal clusters are possible and possesses lower energy
barrier. However, the energy for the desorption of CO and CO2 were found to be
significantly large. Moreover, the formation of CH4 or CH3OH as a side reactions at
room temperature indicates yet another potential application of the designed systems.

[1] Pala, M.; Ugolini, D.; Ceppi, M.; Rizzo, F.; Maiorana, L.; Bolognesi, C.;
Schilir, T.; Gilli, G.; Bigatti, P.; Bono, R.; Vecchio, D, 32 121-126 (2008).
[2] IARC Monographs on the Evaluation of Carcinogenic Risks to Humans,WHO,
Lyon 88, (2006).
Contact:jcjiang@mail.ntust.edu.tw

146

Catalytic Enhancement of the Dehydrogenation of Propane


to Propylene on Rhodium Nanoclusters (Rh 13 ) Supported on
Unzipped Graphene Oxide A DFT Study
Chun-Chih Chang1 and Jia-Jen Ho
1

Department of Chemistry, National Taiwan Normal University


No. 88, Section 4, Tingchow Road, Taipei 116, Taiwan

The catalytic activity of rhodium nanoclusters (Rh 13 ) on unzipped graphene oxide


(Rh 13 /UGO)[1] has been investigated for comparison with Rh 13 nanoclusters. The
binding energy of Rh atoms on UGO is less than the cohesive energy (- 5.75 eV) of
bulk Rh, indicating that the Rh atoms adsorbed on UGO tend to collect into clusters.
We calculated the energies of adsorption of C 3 H 8 on Rh 13 -Ls /UGO Rh 13 (where the
L s representing low symmery shape of Rh 13 nanocluster on unzipped graphene oxide)
to have the largest energy, -0.42 eV, with CH bonds of methyl (CH 3 ) and methylene
(CH 2 ) being elongated from 1.094 to 1.148 and 1.102 to 1.150, respectively. Our
proposed reaction path for the dehydrogenation of propane to propylene[2] on Rh 13 L s /UGO, has the first barrier of 0.22 eV for dissociating the C-H bond of methyl
group to form propyl (C 3 H 7 ), and the subsequent C-H bond scission on the 2nd degree
carbon of methylene group to form propylene has an even smaller barrier of 0.16 eV.
The Rh 13 -Ls /UGO might act as an effective catalyst to adsorb and to activate the
scission of the C-H bonds of propane. The calculated data required to support all
evidence of this result, including the electronic distribution and the density of states
of adsorbed propane on Rh 13 -Ls /UGO, are provided.

[1] X. Cao, Y. Ji, and Y. Luo, J. Phys. Chem. C 119, 1016-1023 (2015).
[2] C. C. Chang, J. J. Ho, Phys. Chem. Chem. Phys. 17, 11028-11035.(2015)

Contact: corresponding author email address here

147

Methane and Ethane Oxidative Dehydrogenation


Mechanism on MoO 3 and Transition Metal Doped MoO 3
Surfaces
Chen-Cheng Liao, Yao-Shun Zhan, Yu-Te Chan, Ming-Kang Tsai*
Department of Chemistry, National Taiwan Normal University, Taipei 10677, Taiwan
Massive production of shale gas becomes technologically accessible due to the
development of horizontal drilling and hydraulic fracturing in the recent years, especially in
United States. The global energy supply is therefore significantly reshaped in respect to the
cost of liquefying shale gas for intercontinental transport. With the fact that the primary
composition of shale gas is methane or ethane, converting these alkane into other derivatives
play a crucial role to the current energy market. The recent experiment carried out by
Al-Hazmi et al. showed the use of Mo-V-Mn-W catalyst for ethane oxidative
dehydrogenation (ODH) to produce ethylene in short contact time.1 With varying the tungsten
loading, different selectivity of ethylene production ratios were observed. Therefore, the
present study used the first-principles calculations to compare the potential ethane
dehydrogenation reaction mechanism on MoO 3 surface and other V, W doped MoO 3 surfaces.
The minimum energy pathway of producing ethylene as well as other potential chemical
product is discussed. The electronic structure effect introduced by V and W dopants are
analyzed.
_p y_

Reference

Mohammed H. Al-Hazmi,1 Taiwo Odedairo,1,2 Adel S. Al-Dossari,1 and YongMan


Choi1, "Revisiting Oxidative Dehydrogenation of Ethane by W Doping into MoVMn Mixed
Oxides at Low Temperature," Adv.Phys.Chem . 2015, 102583 (2015)
Contact: mingkang.tsai@gmail.com

148

Combined Experiment and DFT Investigations of FePt


Nanodentrites with High-index Facets as Active
Electrocatalysts for Oxygen Reduction Reaction
Hung-Lung Chou,1,a,* Di-Yan Wang,1,b,c* Ching-Che Cheng,c Yu-Han Wu,c ChinMing Tsai,c Heng-Yi Lin,c Yuh-Lin Wang,b Bing-Joe Hwang,d,e Chia-Chun Chen,b,c
a

Graduate Institute of Applied Science and Technology, National Taiwan


University of Science and Technology,Taipei 106, R.O.C
b
Institute of Atomic and Molecular Science, Academia Sinica, Taipei 106, Taiwan
c
Department of Chemistry, National Taiwan Normal University,Taipei 106,
Taiwan
d
Nanoelectrochemistry Laboratory, Department of Chemical Engineering, National
Taiwan University of Science and Technology, Taipei 106, Taiwan
e
National Synchrotron Radiation Research Center (NSRRC), Hsinchu 300, Taiwan

In this study, three different types of alloyed FePt nanostructures, nanodendrites,


nanospheres and nanocubes, were prepared and their catalytic activities for oxygen
reduction reaction (ORR) were studies. The ORR catalytic activity of the
nanostructures was increased in the order of E-TEK Pt/C < FePT nanospheres < FePt
nanocubes < FePt nanodendrites. In particular, a cation exchanging reaction was
developed for the preparation of FePt nanodendrites, consisting of a dense array of
branches on a core. The FePt nanostructures were analyzed by high-resolution
transmission electron microscopy (HRTEM), high angle annular dark field (HAADF),
scanning transmission electron microscopy (STEM) and electron energy loss
spectrum (EELS) mapping. The HRTEM images revealed that the large surface area
of FePt nanodendrites with a high density of atomic steps was enclosed by high-index
{311} facet. The density functional theory simulation was performed to understand
the origins of the enhanced electrochemical activity of FePT nanodendrites. The
enhancement could be attributed to the exposure of high-index {311} facet of the
nanodendrite with high surface energy in comparison to that low-index {111} and
{200} facets of FePT nanoshperes and nanocubes, respectively. Our experimental and
theoretical studies have opened a route toward the syntheses of new nonprecious
alloyed nanostructures to replace Pt as active fuel cell catalysts.
[1]
[1] Nano Energy, (2015), 11, 631-639.
Contact: HLCHOU@mail.ntust.edu.tw
Acknowledgement:
We thank the NCHC and NTUST for providing massive computing time. Financial
support from the National Science Council under Contracts No. NSC 102-2221-E011-025 and MOST 103-2221-E-011-041 are also gratefully acknowledged.

149

Density-functional Calculations of Methane Conversion on


Platinum Decorated Graphene Oxide Sheets
Shiuan-Yau Wu, Chien-Hao Lin, and Jia-Jen Ho *
Department of Chemistry, National Taiwan Normal University, City, Taiwan

Based on density functional theory (DFT) calculation, we have investigated methane


conversion on two platinum atoms supported with graphene oxide sheet (Pt 2 /GO). In our
calculation, CH 4 molecule could be adsorbed surrounding the Pt atoms of the Pt 2 /GO sheet
with adsorption energies within 0.11 ~ 0.53 eV, together with the elongated CH bond
causing small CH 4 dehydrogenation energy barrier of 0.33 eV; all these indicated that Pt atom
on GO sheet could activate CH 4 molecule to form CH 3 + H. The CH 3 would further
dehydrogenate to form CH 2 , bridging on two Pt atoms in the absence of oxygen molecule.
However, when the oxygen molecule was added onto the Pt 2 /GO sheet to form a Pt 2 O 2
structure on surface, the methanol formation (Pt 2 O 2 + 2CH 4 Pt 2 + 2CH 3 OH) would
proceed in accompany with the restoring of the original Pt 2 /GO sheet. In addition, the role of
GO sheet in the CH 4 activation was identified by the electronic density analysis, in which that
epoxy groups of GO sheet could change the d-band structure of Pt atoms, generating several
independent peaks of d z 2 state over the Fermi level, and these peaks could perform a great
interaction with the CH bonding orbital of CH 4 molecule [1].

[1] C. C. Wang, S. S. Siao, and J.-C. Jiang, J. Phy. Chem. C 116, 6367 (2012).

Contact: jjh@ntnu.edu.tw

150

Ammonia synthesis by Nitrogen and Hydrogen on


W(111)surface:A Computational Study
Guan-Ying Li, Chu-Han Chung, Chia-Ni Li, Hui-Lung Chen
Department of Chemistry and Institute of Applied Chemistry, Chinese Culture
University, Taipei, 111, Taiwan

In recent years, large number of petroleum is used in the transportation industry. These
petroleum products contain nitrogen in heterocyclic structures comprising pyridine and
pyrrole ring system.[1] The ammonia has a high hydrogen content (17.7 wt.%) and high
energy density (3000 Wh/kg). Therefore NH 3 provides a promising mode of the transfer and
stored of hydrogen for its on-site generation.[2] Therefore in our study, we interested
hydrogenation nitrogen gas to form NH 3 . The adsorption and hydrogenation behavirs of
nitrogen gas on W(111) surface have been studied by employing spin-polarized density
function theory calculations (DFT) with Vienna ab initio Simulation Package (VASP). In this
work, three adsorption sites of the W(111) surface were considered, such as top (T), 3-foldshallow (S) and 3-fold-deep (D) sites. The most stable structures of N 2 and each N x H y
species on the W(111) surface have been predicted. The hydrogenation process were studied
with nudged-elastic-band (NEB) method, which was applied to locate transition structures,
and minimum energy pathways (MEP), which were constructed accordingly. Vibrational
frequencies of the adsorbed structures were analyzed by diagonalizing the hessian matrix of
selected atoms within the VASP approach. In our calculation, we find the rate-determing step
is at the TS1 with the activition energy of 40.9 kcal/mol. All the information predicted

about the reaction mechanism, the catalytic activity of various surface sites, would be
difficultly to achieve with experimental measurements, indicating that the periodic
DFT calculations might play a essential role in the future strategic design of highperformance catalytic surfaces for the hydrogenation of N 2 .

[1] Y. Ninomiya, Z. B. Dong, Y. Suzuki, and J. Koketsu, Fuel 79, 449(2000).


[2] M. R. Rahimpour, and A. Asgari, Int. J. Hydrogen Energ. 34, 5795(2009).

Contact: chl3@faculty.pccu.edu.tw

151

Computational study of hydrogen storage in quasi-2


dimensional potential well of K-intercalated graphite oxide
layered structure
Jaehyun Bae1, Jisoon Ihm1
1

Department of Physics and Astronomy, Seoul National University, Seoul, Korea

We used both density functional theory (DFT) calculation and classical grandcanonical Monte-Carlo (GCMC) simulations to investigate the theoretical hydrogen
storage capacity on the K-intercalated graphite oxide (KGO). Depending on the
synthesis process, interlayer distance of graphite oxide (GO) can be varied by
controlling the functional group density or introducing alkali metal ion. DFT
calculations show that average hydrogen binding potential inside the KGO layer is
increased by the dipole interaction and small hybridization between hydrogen
molecule and functional groups. Introducing alkali metal ions inside the GO layers
further increases average binding potential by ~0.1eV and enlongates interlayer
distance.
In the grand-canonical Monte-Carlo simulations, we used DFT calculation fitted H 2 KGO and H 2 -H 2 interaction potential and simulation results are understood by
equilibrium of interacting gases in the quasi 2-dimensional potential well inside the
KGO layers. Hydrogen storage capacity of KGO reaches 3wt% at 300K and 10MPa.
Our computational study suggests the best way of synthesizing the optimal chemical
and atomic structure of KGO for hydrogen storage medium.

Contact: J. Bae (jbae137@gmail.com)

152

Tetrahedral Silsesquioxane Framework: A Feasible Candidate


for Hydrogen Storage
Amol Deshmukhab, Yun-Wen Chena and Jer- Lai Kuoa*
Institute of Atomic and Molecular Science, Academia Sinica ,Taiwan.
b
National Central University, Taiwan.

The increasing demand for energy supply in global civilization and rising population make
human to explore more energy resources. [1] The search for new materials that can withstand
tough demands of practical hydrogen storage for use in automotive transportation is currently
receiving great deal of attention from the scientific community.[2] In this work, the hydrogen
storage capacity of transition metals decorated boron doped tetrahedral silsesquioxane
frameworks (B-TSF) are investigated using first principles density functional theory
calculations. We show that boron substitution into the benzene ring of tetrahedral
silsesquioxane framework (TSF) linker substantially enhances the transition metals
adsorption energy to the linker as well as maintains stable hydrogen adsorption energy to
transition metals. It is found that average hydrogen binding energies in Sc, Ti and V
decorated B-TSF are 0.29 eV, 0.40 eV and 0.57 eV respectively with decent gravimetric
density of 7, 5.6 and 5.44 wt%. Free energy calculations are also carried out to estimate the
working temperature and pressure for hydrogen storage using TSF.
Fig. B-TSF and Temperature dependence of average adsorption energy with Gibbs free energy correction for MB-TSF (M= Sc, Ti and V) at a) 100 bar

References:

1. Schlapbach, L and Zuttel A. Nature, 2001. 414, 353.


2. Xiao-Dong Li, Hong Zhang, Yoshiyuki Miyamoto, Yong-Jian Tang, Chao-Yang Wang,
Struct Chem 2014, 25, 177-185
Contact: damol92@gate.sinica.edu.tw

153

Influence of non-local van der Waals corrections on the bulk


and surface properties of pristine metals
Ji-Hwan Lee, Ji-Hyun Lim, and Aloysius Soon
Global E3 Institute and Department of Materials Science and Engineering,
Yonsei University, Seoul, South Korea

Current state-of-the-art materials-related calculations typically employ the KohnSham density-functional theory (DFT), commonly using the local-density and
generalized gradient approximations for the exchange-correlation (xc) functional.
These (semi-)local xc functionals have demonstrated to be very successful in
describing the local atomic geometry and energetics of various materials ranging
from gases, liquids, and bulk solids. The level of accuracy in such DFT-based
approaches to studying the electronic structure of these materials, however, largely
depends not only on the employed approximation to the xc potential but also upon the
system which is being investigated. The difficulties, for instance, in arriving at a
reasonable description of van der Waals (vdW) interactions by such DFT-based
models, is to date a big challenge. This stems from the well-known fact that such
vdW interaction is intrinsically a non-local correlation effect which is not captured in
the commonly deployed (semi-)local xc functionals. In this work, using various
flavours of vdW-corrected DFT xc functionals, we systematically study the bulk and
surface properties of various pristine metals (consisting a range of fcc, bcc, and hcp
metals), and critically assess the reliability of the different vdW-corrected DFT
methods in describing these important physio-chemical properties.

Contact: Aloysius Soon (aloysius.soon@yonsei.ac.kr)

154

Raman spectra - crystal packing structures relationship in


P3HT: A first-principles DFT investigation
Sainbileg Batjargal,1 and Michitoshi Hayashi2
1

Center of Condensed Matter Sciences, National Taiwan University, Taipei


106,Taiwan
2
Molecular Science and Technology Program, Taiwan International Graduate
Program, Academia Sinica,Taipei 106, Taiwan

Semiconducting poly(3-hexylthiophene) [P3HT] polymers have gained great attention


in developing flexible optoelectronic devices with low fabrication costs, such as
organic solar-cells, field-effect transistors and light-emitting diodes. Morphology and
packing of crystal structure in P3HT can have impact on their functional properties
(i.e. electrical, optical and vibrational). Understanding of how the packing
configuration of the crystal conformations of P3HT affect on Raman spectra and
Raman modes is lacking because computational investigations of this relationship
have been untaken on crystalline structures as polymer with periodic boundary
condition (PBC). Thus in this study, we investigate, by performing the first-principle
simulations based on the density functional perturbation theory (DFPT), that how the
origin of the characteristic Raman spectra can be related to the packing configuration
of the crystal conformations of regioregular P3HT (rr-P3HT) for periodic forms. Our
simulation results indicate that the intense peaks (modes) of Raman spectra in rrP3HT are strongly correlated with the planarity and the torsional conformation of the
conjugated backbone rings in the packing. In particular, the intense Raman peaks of
rr-P3HT appear around 1397 and 1411 cm-1 and these are attributed to in-plane C-C
and C=C streching vibration of the conjugated backbone rings in the packing planar
configuration in which P3HT layers are stacked parallel to each other. In the
nonplanar torsional conformation in which the backbone rings in P3HT layers are
rotated by 120 dihedral angles to each other, the backbone planarity decreases and
then C=C peak splits into two peaks at 1436 and 1450 cm-1. At the same time, the CC peak position is shifted to the lower wavenumber (lower energy) at 1375 cm-1.
These changes can be originated from the redistribution of -electron density within
stacking of rr-P3HT layers due to the rotation of the conjugated backbone
rings reduces the overlap of molecular orbitals.

Contact: sc.batjargal.s@gmail.com

155

Structural and Magnetic Properties of Zn 0.5 Co 0.5 O Alloy


Configurations via DFT
Alexandra B. Santos-Putungan1,2 and Francis Norman C. Paraan2
1

National Institute of Physics, University of the Philippines Diliman, Philippines


2
Materials Science and Engineering Program, University of the Philippines
Diliman, Philippines

We studied the structure and magnetic properties of ZnCoO alloy configurations via
spin-polarized density functional theory (DFT). For the hexagonal wurtzite
Zn 0.5 (Co) 0.5 O, we used a 1 x 1 x 1 ZnO unit cell in a 4-atom bilayer configuration,
with one Zn atom replaced by Co. In the similar manner, we utilized a 1 x 1 x 1 CoO
rocksalt structure, with four Co atoms replaced with Zn to obtain Co 0.5 (Zn) 0.5 O. We
found that the original ZnO lattice did not change appreciably upon Co alloying, with
around 2% compression, and thus the structure remains robust and atoms bond
stronger. This is complemented by Zn 0.5 (Co) 0.5 Os stronger bulk cohesive energy per
formula unit (8.29 eV) compared to bulk ZnO (7.05 eV). Additionally, minimal
charge redistribution between the metal atoms and oxygen is observed. On another
note, a volume expansion of 3% was observed for Co 0.5 (Zn) 0.5 O, implying the
formation of weaker bonds between atoms. The calculated bulk cohesive energy per
formula unit for CoO is 9.47 eV, quite larger than that of Co 0.5 (Zn) 0.5 O at 8.07 eV.
Lastly, our calculations showed that the net magnetization of ZnO upon Co alloying
is enhanced significantly, while the reverse is true for Zn-alloyed CoO. The results
suggest that Zn 0.5 (Co) 0.5 O is more stable in hexagonal wurtzite structure, and could
be a better controllable ferromagnetic material for spintronics applications.

Contact: asantos@nip.upd.edu.ph

156

Ab initio-aided thermodynamic reassessment of the Mo-Zr


binary system
M. Anshar Makhraja1 and Shih-kang Lin1,2,*
1

International Curriculum for Advanced Materials Program, National Cheng


Kung University, Tainan 70101, TAIWAN; 2Department of Materials Science and
Engineering, National Cheng Kung University, Tainan 70101, TAIWAN.
A new set thermodynamic parameters of the Mo-Zr system was constructed by using
ab initio-aided CALPHAD (calculation of phase diagram) method. The ordered
laves_c15 phase was described based on the compound energy formalism with
(Mo,Zr) 2 (Mo,Zr) model. The ab initio energetics of the Mo 2 Mo, Mo 2 Zr, Zr 2 Mo, and
Zr 2 Zr end-members as well as the body centered cubic (bcc) and hexagonal close
packed (hcp) solid solution phases were calculated. Special quasirandom structures of
the bcc and hcp solution phases with three compositions, namely Mo 0.25 Zr 0.75 ,
Mo 0.5 Zr 0.5 , and Mo 0.75 Zr 0.25 , were taken to calculate ab initio mixing energies of the
solution phases at 0 K. Redlich-Kister polynomial was used to fit the ab initio mixing
energies for obtaining the temperature-independent excess Gibbs free energies of the
bcc and hcp phases. All available experimental information on phase equilibria and
thermodynamic properties of the Mo-Zr binary system was critically reviewed; they
were used to optimized the temperature-dependent contributions on phase stability of
the Mo-Zr system using the CALPHAD method. The proposed thermodynamic model
of the laves_c15 phase was with less number of interaction parameters than other
recent assessments. The calculated phase diagram agrees closely with experimental
data. The thermodynamic model of the Mo-Zr binary system can be further integrated
with high-order alloy system.

Contact: E-mail: linsk@mail.ncku.edu.tw

157

The First-principles Mapping onto the Phase Field


Crystal Model
Swastibrata Bhattacharyya,1 Kaoru Ohno,1 and Ryoji Sahara2
1

Department of Physics,Yokohama National University, Yokohama, Japan


2
National Institute for Materials Science (NIMS), Tsukuba, Japan

Understanding microstructures, formed during various processing conditions of


materials, is very important in predicting their durability and performance in different
applications. These microstructures play an important role in determining many
material properties such as strength, ductility, hardness, corrosion resistance,
wearability and temperature behavior to name a few. First principles methods such as
density functional theory (DFT) [1], [2] cannot be used to study such phenomena due
to the limitation of the maximum number of atoms. Phase field models (PFM) [3]
such as phase field crystal (PFC) model [4], [5] , offer a powerful tool to study the
growth of crystals by including a periodic field into the standard PFM. However, it is
a purely empirical approach and there is no direct connection between this model and
the first principles methods. As a result PFM is not been widely accepted in various
industries [6]. The purpose of our study is to bridge these two different methods to
justify the phase field model from the viewpoint of the first principles theory.
Because the PFC model is based on the classical DFT [7], we will discuss the
connection between these two theories. There is a problem in making this connection
concerning the inconsistency with the continuity equation. We will propose an idea to
overcome this difficulty. We calculate the total energy of the system from first
principles and then obtain the free energy by taking the local trace of the total energy
with respect to the atomic coordinates in a length scale less than the interatomic
distances as explained in Ref. [8]. We also have considered the effect of temperature
in this method. Although not a unique, we present a possible way to map onto the
PFC model from first principles. We use this model to study time evolution of a
cluster in vacuum or liquid and will present some initial results.
[1] P. Hohenberg and W. Kohn, Phys. Rev. 136, B864 (1964).
[2] W. Kohn and L. J. Sham, Phys. Rev. 140, A1133 (1965).
[3] A. A. Wheeler, W. J. Boettinger and G. B. McFadden, Phys. Rev. A 45,
7424 (1992).
[4] K. R. Elder, M. Katakowski, M. Haataja and M. Grant, Phys. Rev. Lett. 88,
245701 (2002).
[5] K. R. Elder and M. Grant, Phys. Rev. E 70, 051605 (2004).
[6] L-Q. Chen, Chin. Sci. Bull. 59, 1641 (2014).
[7] T. V. Ramakrishnan and M. Yussouff, Phys. Rev. B 19, 2775
(1979).
[8] Y. Misumi, S. Masatsuji, R. Sahara, S. Ishii, and K. Ohno, J. Chem. Phys.
128, 234702 (2008).
Contact: ohno@ynu.ac.jp

158

Hybrid Functional Calculation of Defects in Pseudo-Binary


Indium Oxynitride
K. Amnuyswat,1 P. Thanomngam,1,2
1

College of Nanotechnology, King Mongkuts Institute of Technology Ladkrabang,


Bangkok, Thailand
2
Thailand Center of Excellence in Physics, Commission on Higher Education,
Ministry of Education, Bangkok, Thailand

Indium oxynitride (InO x N y ) is an attractive material that shows multifunctionality


in electronic and optical applications due to its wide range tunable band gap.
However there were only few studies available for this interesting material, especially
on defect structure and its associated electronic property. In this work, first-principles
calculation based on Density Functional Theory (DFT) within the Heys, Scuseria and
Ernzerhof (HSE) hybrid functional for exchange-correlation energy was performed to
investigate atomic structure, electronic properties and role of oxygen (O) defects
occurred in a pseudo-binary InO x N y by means of their defect formation energy. The
defect formation energy of both substitutional and interstitial O sites was compared
with all possible native point defects in InN. Our results revealed that O atom prefers
to substitute in N site since it has lowest formation energy for all equilibrium crystal
growth conditions. This result is consistent with the experimental observations of
pseudo-binary InO x N y prepared by RF magnetron sputtering method.[1-3] Moreover,
the energy gap of InN calculated by HSE method is 0.710 eV. The HSE calculation
showed that the O substitution slightly widening the InN band gap to 0.766 eV while
the N vacancy gives wider InN band gap of 1.410 eV. The complex defect of N
vacancy and O substitution was also performed and discussed. The results of N
vacancy and complex defect calculations provided well explanation on wide energy
gap of InN fabricated by traditional sputtering method. [1, 4-5]

[1] A. Sungthong, S. Porntheeraphat, A. Poyai and J. Nukeaw, Appl. Surf. Sci.


254 (23), 7950-7954 (2008).
[2] K. Amnuyswat, C. Saributr, P. Thanomngam, A. Sungthong, S.
Porntheeraphat, S. Sopitpan and J. Nukeaw, X-Ray Spectrometry 42 (2), 8792 (2013).
[3] J. T-Thienprasert, J. Nukeaw, A. Sungthong, S. Porntheeraphat, S. Singkarat,
D. Onkaw, S. Rujirawat and S. Limpijumnong, Appl. Phys. Lett. 93 (5),
051903 (2008).
[4] Motlan, E. M. Goldys and T. L. Tansley, J. Cryst. Growth 241, 165-170
(2002).
[5] M. Sparvoli, R. D. Mansano and J. F. D. Chubaci, Materials Research 16, 850852 (2013).
Contact: kakittip@kmitl.ac.th

159

A first-principles study of the mechano-thermodynamics of


super-ultrahard materials
Yong-Hyuk Lee, Ji-Hwan Lee, and Aloysius Soon
Global E3 Institute and Department of Materials Science and Engineering,
Yonsei University, Seoul, South Korea

Having a deep understanding of the various physio-chemical factors to control the


phase stability of functional materials has long been the holy grail of fundamental
materials research. This includes the ability to manipulate and isolate useful
metastable phases of functional materials via physical stress/strain to the material
system, or simply regulating its immediate chemical growth environment. Ab initio
electronic structure calculations have shown to be an effective approach to investigate
and study the phases of any proposed crystal structure and the fundamental
knowledge gained from these studies can greatly boost the power to further design
new materials with desired properties. In this work, we will use examples of
technologically important superhard functional materials (namely, diamond and
titanium nitride) to illustrate how first-principles density-functional theory
calculations can be used to study (i) the phase transformation of diamond to graphite
via applying mechanical strain, and (ii) the phase stabilities of various stoichiometries
of titanium nitrides under various chemical growth conditions.

Contact: Aloysius Soon (aloysius.soon@yonsei.ac.kr)

160

Numerical Calculation on Controlled Oscillatory Cracks in


Glass Film on Substrate
Jong Hyun Jung,1 Seungwook Son,1 Jisoon Ihm1
1

Department of Physics and Astronomy, Seoul National University, Seoul, 151742, Republic of Korea

When a film on a substrate is heated, due to thermal expansion mismatch, cracks may
form in the film. The crack is sometimes oscillatory and can be controlled to
propagate on a pattern [1, 2] or void remained by removing the pattern. The aim of
this study was to investigate its mechanism. The oscillatory propagation of the cracks
was calculated by the extended finite element method. The oscillatory path of
propagating crack was accurately reproduced. We suggest that the crack is confined
on the void because the crack turns away from the boundary of void, an area
effectively softer than the outside. This controlled formation of cracks has potential
use in the nanopatterning of electronics and microfluidics.

[1] D. Kim, P. Makaram, and C. V. Thompson, Appl. Phys. Lett. 97, 071902
(2010).
[2] B. Chen, and D. A. Dillard, Int. J. Solids Struct. 38, 6907-6914 (2001).

Contact: jjhjm17@snu.ac.kr

161

First-Principle Characterization for Electronic


Coupling in Singlet Fission
Chou-Hsun Yang1and Chao-Ping Hsu1
1

Institute of Chemistry, Academia Sinica, Taipei, 115 Taiwan

The electronic coupling for singlet fission, an important parameter for


determining the rate, has been found to be too small unless charge-transfer (CT)
components were introduced in the diabatic states, mostly through perturbation or a
model Hamiltonian.

In the present work, the Fragment Spin Difference (FSD)

scheme was generalized to calculate the singlet fission coupling. The largest coupling
strength obtained was 14.8 meV for two pentacenes in a crystal structure, or 33.7
meV for a transition-state structure, which yielded singlet fission lifetime of 239 or 37
fs, generally consistent to experimental result (80 fs). Test results with other
polyacene molecules are similar. We found that the charge on one fragment in the S1
diabatic state correlates well with FSD coupling, indicating the importance of the CT
component. When the CT state energy is lower and close to S 1 state, it is likely to
have a better singlet fission coupling. The FSD approach is a useful first-principle
method for singlet fission coupling, without the need to include the CT component
explicitly.

[1] Chou-Hsun Yang and Chao-Ping Hsu, J. Phys. Chem. Lett. 6, 1925 (2015).

Contact: jeffyang@sinica.edu.tw

162

Theoretical Investigation of Charge Transfer


Processes at Pentacene-C 60 Interface
Bo-Chao Lin1, Brian T. Koo2, Paulette Clancy2 and Chao-Ping Hsu1
1 Institute of Chemistry, Academia Sinica, Taipei, Taiwan.
2 School of Chemical and Biomolecular Engineering, Cornell University, Ithaca, USA
1

Institute of Atomic and Molecular Sciences, Academia Sinica, City, Country


2
Department of Physics, National Taiwan University, City, Country

Photovoltaic devices have great potential in harvesting solar energy.1 In organic solar
cells, the role of the donor-acceptor heterojunction is critically important; here optical
excitation leads to charge separation (CS) and subsequently, photocurrent generation.
Charge recombination (CR) may also happen, which reduces the overall efficiency of
the device. After light absorption, the singlet excitation of a pentacene can achieve CS
at the interface, or it may also undergo singlet fission and produce two triplet excitons,
which may further undergo CS at the interface.2 In this work, we study charge
transfer processes at the pentacene-C 60 interface, including CS rates in both singlet
and triplet surfaces, and the CR rate back to the ground state. We first constructed two
different pentacene-C 60 interfacial structures by force field optimization.3 With
pentacene-C 60 molecular pairs derived from the structures, we calculate the electronic
couplings of CS and CR reactions. We found that the electron transfer couplings have
a systematic preference on the configurations. Both singlet and triplet CS coupling
prefer to take place in the head-on configurations where the C 60 is located at the top
of the pentacene, whereas CR coupling prefers the ``inserted'' configuration, where
the pentacene is located between two C 60 and is slightly lifted from the layer. In
estimating the electron transfer rates, we found that the interfacial energy shift has a
determining effect. When an interfacial energy derived from experimental results is
included, we found that the calculated triplet CS rate can reach 1013 s-1, while the
singlet CS rate is only about 105 s-1. The CR rate was calculated to be 1011 s-1 for a
singlet ion pair. Our results indicate that triplet CS is fast. Since triplet CS can
proceed after singlet fission, without immediate recombination, it is important for
photovoltaic performance in the pentacene-C 60 system studied.

[1] S. Yoo, B. Domercq, B. Kippelen, Appl. Phys. Lett. 85, 5427 (2004)
[2] W. L. Chan, M. Ligges, A. Jailaubekov, L. Kaake, L. Miaja-Avila, X. Y. Zhu,
Science 334, 1541 (2011)
[3] A. Al-Mahboob, J. T. Sadowski, Y. Fujikawa, T. Sakurai, Surf. Sci. 603, L53
(2009)
Contact: dos@gate.sinica.edu.tw

163

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