Article

pubs.acs.org/JPCA

Ab Initio Investigation of O−H Dissociation from the Al−OH2

Complex Using Molecular Dynamics and Neural Network Fitting
Thi H. Ho,† Nguyen-Nguyen Pham-Tran,‡ Yoshiyuki Kawazoe,§,∥ and Hung M. Le*,⊥,#
†
Department of Materials Science, University of Science, Vietnam National University, Ho Chi Minh City, Vietnam
‡
Department of Chemistry, University of Science, Vietnam National University, Ho Chi Minh City, Vietnam
§
New Industry Creation Hatchery Center, Tohoku University, Sendai City, Japan
∥
Thermophysics Institute, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia
⊥
Computational Chemistry Research Group, Ton Duc Thang University, Ho Chi Minh City, Vietnam
#
Faculty of Applied Sciences, Ton Duc Thang University, Ho Chi Minh City, Vietnam

ABSTRACT: The dissociation dynamics of the O−H bond in

Al−OH2 is investigated on an approximated ab initio potential
energy surface (PES). By adopting a dynamic sampling
method, we obtain a database of 92 834 configurations. The
potential energy for each point is calculated using MP2/6-
311G (3df, 2p) calculations; then, a 60-neuron feed-forward
neural network is utilized to fit the data to construct an
analytic PES. The root-mean-square error (rmse) for the
training set is reported as 0.0036 eV, while the rmse for the
independent testing set is 0.0034 eV. Such excellent fitting
accuracy indeed confirms the reliability of the constructed
PES. Subsequently, quasi-classical molecular dynamics (MD)
trajectories are performed on the constructed PES at various
levels of vibrational excitation in the range of 1.03 to 2.23 eV
to investigate the probability of O−H bond dissociation. The
results indicate a linear relationship between reaction
probability and internal energy, from which we can determine
the minimum activation internal energy required for the
dissociation as 0.62 eV. Moreover, the O−H bond rupture is
shown to be highly correlated with the formation of Al−O
bond.

I. INTRODUCTION which was previously shown to play a role in splitting water to

Over the past few decades, the research of alternative
replacements for fossil fuel has become a leading interest
because of gradual depleting of natural oil and the consequence
of environmental pollution. There are yet many solutions for
substituting energies such as eco fuels,1 solar energy,2,3 and
wind energy. Nowadays, hydrogen fuel is regarded as one of the
effective power solutions. It has been proved that hydrogen fuel
plays a meaningful role in providing a sustainable environment4
and has noticeable applications in power generation for public
transporting vehicles. Moreover, the significance of hydrogen
storage for the utilization in cellular devices, portable
electronics, and emergency power supply5−7 is also recognized
even though there are still technical difficulties with hydrogen
storage. Recently, we have seen some great progress made
toward hydrogen production and storage. In the content of the
present theoretical study, we focus on the activity of atomic Al,
produce hydrogen.8
Lightweight aluminum is abundant on Earth and considered
as an excellent material for hydrogen generation.9 As a result,
the concept of producing hydrogen by the reaction of
aluminum with water has greatly attracted researchers for
years. In practice, the use of neutral aluminum surface in
hydrogen production has been considered to be effective. For
instance, the theoretical yield of H2O dissociation activated by
aluminum was reported to be 5.6 wt %, which approached the
6% standard set by the U.S. Department of Energy;10 however,
the activity of catalyst in this situation might be destructed
rapidly because of surface passivation. An alternative solution to
Received: September 29, 2015
Revised: December 8, 2015

© XXXX American Chemical Society A DOI: 10.1021/acs.jpca.5b09497

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improve the catalytic activity is the use of aluminum
nanoparticles. There have been studies showing that it is
possible to generate a large amount of pure hydrogen by
employing the hydrolytic reaction of highly activated aluminum
nanoparticles in water.11−13 In addition, the use of Al
nanoparticles alloyed with Li was reported to facilitate the
reaction yield in a theoretical study.14 Using the density
functional theory (DFT)15,16 approach, Liu et al.17 reported the
reaction barrier of H2O dissociation to fall in the range of 0.83
to 2.12 eV, depending on the size of Al cluster in use.
In this study, we put more concern on the theoretical
mechanism of the single-Al-atom catalysis. Basically, the
reaction mechanism involving atomic aluminum in the ground
electronic state (2P0) is referred to as aluminum oxidation.18,19
A study reported by Sharipov et al.8 suggested four elementary
steps
Al + H 2O → HAlOHtrans (1)
HAlOHtrans → HAlOHcis (2)
HAlOHtrans/cis → AlOH + H (3)
AlOH + H → AlO + H 2 (4)
Considering the fact that limited data have been reported on
the reaction kinetics of Al with H2O, we believe that it is worthy
to conduct a fundamental study regarding the reaction
dynamics of aluminum with water to produce hydrogen. In
the content of the present study, we conduct a MD
investigation of Al+H2O at various levels of vibrational
excitation on an analytic PES constructed by numerical fitting
of ab initio data.
The quantum-mechanical approach, based on solving the
Schrodinger equations for many-electron systems, is known as a
powerful, effective, and appropriate tool to investigate
elementary reactions. This methodology makes it possible to
explore PES20−22 and local minima23,24 and determine possible
reaction channels and final products of elementary chemical
reactions.25−27 The construction of PES is important because it
can be employed to extract structural properties of many-body
systems, find global (and/or local) minimum energy shapes of
PES of a molecule, and compute reaction rates of chemical
reactions.28
Nowadays, there are numerous methods for constructing a
PES. One of the efficient methods is neural network (NN)
fitting, which is a powerful and robust numerical approximation
technique in chemical reaction dynamics studies.29 In general,
NN can be used to fit the potential-energy database obtained
from ab initio electronic structure calculations. This method
was first proposed to describe surface diffusion in the CO/
Ni(111) system.30 Nowadays, there have been many studies of
complex systems using the NN method to construct PES, such
as the studies of graphite-diamond phase coexistence,31
complex water system, 32 and oxygen dissociation at
Al(111).33 An update to the recent progress in NN PES
developments can be consulted through several reviewing
efforts.34−36
II. METHODOLOGY
1. Constructing the Database for Potential Energy
Surface Fitting. The PES construction demands an effective
method37 to sample data points from the multidimensional
hyperspace. In recent years, there have been at least two
B DOI: 10.1021/acs.jpca.5b09497
Article
primary sampling methods employed to obtain configuration
points to construct database for PES fitting. One of them is
termed the “novelty sampling” method,38,39 which relies on
MD trajectories, while the other method is operated on a
“gradient sampling” basis,40 in which data is collected based on
the analysis of input gradients. The second method is known to
be independent of MD trajectories.
In general, the dynamic “novelty sampling” approach is an
iterative operation of MD trajectories to create new
configuration points. For the operation of this process, an
initial data set is required, which may be generated by either
performing Born−Oppenheimer direct dynamics or executing
MD trajectories on a temporary empirical PES;41 however,
there might be an alternative approach, which we perform in
the current study. Initially, we obtain a first set of data points by
performing partial optimization scans. The unrestricted second-
order Møller−Plesset perturbation level of theory (MP2)42,43 is
employed to perform ab initio calculations with the 6-311G
(3df, 2p) basis set in the GAUSSIAN package.44 Subsequently,
a temporary PES is constructed by executing an NN fit on the
initial set of data points. At this time, we already have a
temporary PES, on which MD trajectories can be executed to
collect more configurations to be added to the database. The
newly sampled data are then merged with the existing database
until some convergence criteria are attained (those criteria will
be discussed later).
In this part, we will discuss the partial optimization process.
In this procedure, we execute preliminary energy optimization
scans with various constraints for three local-minimum
configurations of the AlOH2 system (the Al+H2O, cis, and
trans configurations as shown in Figure 1a−c). According to
our MP2 calculations, the trans configuration is the most stable
structure (−318.3008 au), while the cis configuration
Figure 1. (a) Initial Al+OH2 configuration with the description of
internal coordinates, (b) trans configuration, (c) cis configuration, and
(d) potential energy barrier for Al−OH2 → trans H−Al−O−H
transformation. Our numerical procedure indicates a potential barrier
of 0.79 eV.
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(−318.2994 au) is 0.04 eV higher in energy, and the Al−OH2
complex (−318.2363 au) has the highest potential energy. We
then validate the reliability of MP2 calculations by performing
additional CCSD(T) calculations45−47 for the equilibrium
configurations. The total energies of Al−OH2, cis, and trans
equilibrium configurations given by CCSD(T) are −318.2658
au, −318.3219 au, and −318.3234 au, respectively. The
CCSD(T) results turn out very consistent in terms of energy
difference and structural geometry. Also, by examining the
doublet and quartet energies, we observe that all configurations
prefer to adopt the doublet multiplicity. The detailed values of
bond lengths and angles for three configurations are given in
Table 1. In total, we execute 15 partial optimization scans, in
Table 1. Bond Lengths and Angles for the Equilibrium Al
+H2O, Trans, and Cis Configurations
Al+H2O trans cis
Al−O bond (Å) 2.228 1.706 1.706
O−H1 bond (Å) 0.961 0.955 0.956
O−H2 bond (Å) 0.961 2.776 2.853
H1−O−Al angle (deg) 122.872 125.675 125.869
H2−O−Al angle (deg)
122.872 31.353 29.247
dihedral angle (deg) 148.609 180.000 0.000
each of which the chemical bond of Al−O or O−H, the
bending angle, or dihedral angle is constrained, while the
remaining structural parameters are accordingly optimized to
obtain lowest energy values. The number of samples obtained
for Al+OH2 and trans configurations is smaller than that for the
cis configuration due to symmetry considerations. For the Al
+OH2 system, we perform partial optimization scans for one
Al−O bond, one O−H bond, one angle of Al−O−H, and the
dihedral angle; for the cis and trans configurations, scans are
executed for one Al−O bond, two O−H distances of different
bonding nature, and two angles of Al−O−H. Even though a
new Al−H bond is established in the cis and trans
configurations, we still consider the previous setup of Al−O
and two O−H bonds for mathematical fitting consistency. The
whole scanning process results in an initial data set of 940
configurations with an upper limit of 3.0 eV in energy. The
choice of this maximum energy is sufficient for our purposes. In
addition, we also investigate the transformation barrier from
Al−OH2 to trans H−Al−O−H. As shown in Figure 1d, our
partial optimization indicates that the barrier is 0.79 eV
(excluding zero-point energy correction).
Let us denote the six scaled z-matrix input parameters ri of
the Al−OH2 system that consist of one Al−O and two O−H
distances, two cosines of Al−O−H bending angles, and cosine
of the dihedral angle (as defined in Figure 1a). The scaled
output parameter is the ab initio potential energy V (eV)
obtained from MP2 calculations. To achieve good fitting
quality, we scale all of these parameters as follows
2(ri − rmin)
rscaledi = −1
rimax − rimin
2(Vi − Vimin)
Vscaledi = −1
Vimax − Vimin
where rimin, rimax and Vimin, Vimax are the minimum and maximum
values of the atomic distances and potential energy,
respectively. All maximum and minimum parameters are listed
Article
in Table 2. Upon the use of eqs 1 and 2, all scaled input and
output data should fall in the range of [−1; 1].
Table 2. Minimum and Maximum Values of Parameters in
the Database
minimum maximum
r1 (Å) 1.405 4.132
r2 (Å) 0.754 6.908
r3 (Å) 0.754 6.908
r4 −0.999 0.997
r5 −0.999 0.997
r6 −1.000 1.000
V (eV) 0.000 2.989
A new quantity that is the distance between data points A
and B is introduced to evaluate data distribution in the 6D
configuration hyperspace of internal coordinates. The distance
is calculated using the equation
6
dAB = ∑ (rA scaledi
− rBscaled )2
i
i=1 (7)
where rAscaledi and rBscaledi are the scaled input parameters of point A
and point B, respectively. The distances between all pairs of
scaled configuration points are calculated. Then, we identify the
smallest distance from one particular configuration to the
remaining data points. Finally, the average minimum distance D
is computed by taking the average of those minimum distances.
A distance analysis constitutes the first judgment for selecting a
new point. When a new point is generated, we calculate its
minimum distance to the existing data. If such a minimum
distance is smaller than D, the new configuration will be
disqualified because we do not want to elevate data density in a
dense region. In other words, this distance criterion helps to
collect more configurations in the unknown (less dense)
regions, which should be distant from the existing data points.
After the construction of the initial set of data, an NN fit with
60 neurons in the hidden layer is executed to construct a
temporary PES. MD trajectories are subsequently performed
with zero-point energy to generate more configuration points.
New configurations are selected if they meet all of the following
criteria:
i. Every element of the scaled input vector of the generated
configuration is in the predefined range of [−1, 1].
ii. The distance criterion described above is met.
iii. The difference between (temporary) NN-predicted
energy and true MP2 energy is >0.01 eV.
The NN-predicted potential energies correlated with the
selected configurations are computed and stored in the
database. MP2 calculations are performed for the new data
points, and the resultant ab initio energies are compared with
the previous NN-predicted energies. Statistically, the NN fitting
algorithm tends to put more focus on a dense region, while the
(5) other regions are fitted with lower quality. Unfortunately, the
dynamic-based sampling method often produces a lot of data
points near the equilibrium regions instead of the important
(6) reactive regions. Hence, we formulate the third qualification
judgment that if the difference between two energy quantities is
larger than 0.01 eV, the configuration will be selected (because
it is poorly described in the database). This criterion results in
the disqualification of configurations, most of which fall around
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Table 3. Number of Data Points Obtained and Selected at Every Iteration

number of points for ab initio number of points added to percentage total points in
step calculations database (%) database note
0 0 0 0 940 initial points
1 6400 611 9.5 1551 sampling at zero-point energy
2 1353 247 18.3 1798
3 5000 3505 70.1 5303
4 576 428 74.3 5731
5 204 95 46.6 5826
6 10 004 6855 68.5 12 681 sampling at 3.0 eV of internal energy
7 10 000 7008 70.1 19 689
8 10 029 6395 63.8 26 084
9 6 693 2647 39.5 28 731
10 630 547 86.8 29 278
11 10 000 7972 79.7 37 250 focusing more on O−H stretching
12 10 000 9167 91.7 46 417

local minima and are already well described by the NN. Even in
rare situations, when there might be some useful points
disqualified due to the third judging criterion, we have a chance
to collect them again in the following data-searching iterations.
In iteration 1, MP2 calculations are executed for 6400
configurations obtained from MD trajectories with an internal
energy of 3.0 eV; however, only 611 new configurations that
meet the qualification criteria are selected and added to the
database. The database after iteration 1 contains 1551
configurations; then, it is duplicated by switching the positions
of two H atoms, which increases the number of data points to
3102. At this point, a new NN fit is constructed and considered
as the latest-updated PES.
Such a procedure is performed iteratively to select more
configurations to be added to the database. Beginning at
iteration 2 forth, we perform two different NN fits with 60
neurons in the hidden layer to construct a new data-qualifying
criterion. This new criterion enables us to rapidly eliminate data
points in the very early stage, thereby eliminating the
computational time required for ab initio calculations. For a
particular configuration, if the two NN-predicted potential
energies are larger than 0.01 eV, there is an obvious
disagreement between the two numerical fits; as a result, such
a configuration should be considered; otherwise, it will be
discarded to save computational time. Like the third criterion
above, this new criterion also allows us to focus more on the
less dense regions.
After executing five sampling iterations, the number of
sampled data points has decreased to 204 when we perform
MD sampling with an internal energy of 3.0 eV. At this point,
we believe that the multidimensional hyperspace has been
almost fully covered at this total energy level. Therefore, more
data points should be selected at higher total energies to find
additional configuration points in the reactive regions. Employ-
ing the similar method, we now change the sampling total
energy to 5 eV (and 8 eV later) to collect more data in two last
iterations (iterations 11 and 12). Moreover, those steps
strongly focus on the stretching of two O−H bonds, which
directly produces atomic hydrogen. Therefore, an additional
constraint is applied on sampled configurations in the MD
trajectory process, in which either O−H1 or O−H2 bond is
required to be >1.6 Å. Because the data sampling process has
almost converged, we now employed the global minimum
distance in criterion (ii) instead of the average minimum
distance D so that more data can be sampled during the last
two iterations.
During MD trajectories in the last iteration, a much longer
integration period is required to obtain a new data point. This
means the process has almost converged. The aae and rmse
given by our NN fit are 0.0031 and 0.0033 eV, respectively,
which shows that the numerically approximated PES achieves
an excellent and reliable fitting accuracy. In this stage, we
believe the converged database can fully describe the O−H
dissociation in the Al−OH2 system. When the sampling process
is complete, a total of 46 417 configurations are obtained to
construct the reactive PES of the AlOH2 system. The database
is then duplicated to 92 834 points due to symmetry
permutations of two hydrogen atoms. The detailed data point
numbers in this study are shown in Table 3.
2. Neural Network Fitting. To construct an ab initio PES,
we utilize the well-developed NN fitting method to perform
numerical approximations. An introduction of NN architec-
tures, features, and properties was discussed in detail by Hagan,
Demuth, and Beale.48 In this work, the ab initio data are fitted
using a two-layer, feed-forward NN. The input layer consists of
six scaled internal coordinates of AlOH2 system, as described in
Figure 1a, while the ab initio potential energy serves as the
targeted output. A model of a two-layer NN is shown in Figure
2. The distances ri and potential energy V are scaled using eqs 1
and 2 to prepare data for the fit.
Figure 2. Typical model of a two-layer feed-forward NN. This network
has six parameters in the input layer, 60 neurons in the hidden layer,
and one final output.

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Figure 3. (a) Distribution of absolute errors for the whole database. (b) Plot of NN-predicted energies versus calculated MP2 energies. (c) Mean-
squared errors of the training, validation, and testing sets during the NN training process.
In the first layer, suppose we have m neurons; then, each
outcome ni of a particular neuron should read
6
ni = ∑ w1 rscaledj,i i
+ b1i for i = 1...m
j=1
where w1 is the “weight” matrix of the first layer of size m × 6
and b1 is an m-element bias vector. A hyperbolic tangent
function, denoted as f, is employed as a transfer function to
provide curvatures to the NN. Finally, the output of the two-
layer network is obtained as
m
Vout = ∑ w2 f 1 ni + b for i = 1...m
i same time, we are also concerned with the possible reaction
i=1
where w2 is a 1 × m weight vector and b is the last bias quantity.
The transfer function for the second layer is just a linear
function. During the fitting process, w1, b1, w2, and b are
optimized so that the NN structure matches the shape of ab
initio potential energy function. The number of neurons in the
hidden layer is selected empirically in conjunction with the
complexity of PES roughness. Initially, a particular number of
neurons is selected to train the network, and fitting accuracy is
evaluated. Such a number is gradually increased until accuracy
satisfaction is reached. More specifically, we look forward to
obtaining a marginal improvement of rmse for the independent
testing set. For the complex system such as six-body vinyl
bromide (CH2CHBr) molecule, the number of neurons used
for the fit was reported as 140. Systems with lower levels of
complexity, such as HONO,49 SiO2,37 and BeH+H2,50 required
only approximately 40−60 neurons to fit the database. In this
work, 60 neurons are employed in the hidden layer. The fitting
process is performed to obtain the best approximated NN
function, and all NN PES parameters are stored for later MD
investigations.
Our final NN fitting is executed using 90% of the data, while
5% serves as a validation set and the remaining serves as an
Article
independent testing set. The training process comprises a
maximum of 1000 epochs by employing the Levenberg−
Marquardt algorithm.51 The testing set does not play any roles
in the training process, while the fitting performance of the
validation set is examined to monitor “overfitting”. The
(8)
overfitting behavior is an important factor, which may cause
bizarre predictions of gradients. To prevent it, we employ the
empirical early stopping method in which the training process is
terminated when the rmse of the validation set increases in 20
consecutive training epochs.
3. Setting up Initialized Samples for MD Trajectories.
Our objective is to accurately determine the reaction
probability with respect to various excitation levels. At the
(9)
paths for H dissociation. To do this, we deliberately examine
dissociation time and how Al−OH2 transforms in sampled
trajectories.
Before conducting an MD investigation, we need to prepare
a configuration with randomized Cartesian momenta and
geometry. First, the Cartesian coordinates of the equilibrium
Al−OH2 structure (see Figure 1a) are assigned; then, the
ground-state vibrational energy is introduced into each
vibrational mode using the projection method,39 so that we
can assume our MD simulations to be quasi-classical. With the
geometry and momenta for the ground state, MD is integrated
for a randomized period of time (with a maximum period of
0.25 ps, twice the longest classical vibrational period given by
Hessian analysis). After this short integration, the vibrational
phases are randomized in the ground electronic state with an
internal energy of 1.77 eV. Subsequently, we employ the
projection method to introduce an excitation energy (in the
range of 1.03 to 2.23 eV) into each vibrational mode with equal
amounts (at this point, we assume the system to behave
classically). Because we are investigating a chemical reaction
caused by excitations of molecular vibrations, the total angular
momentum and translational movement are eliminated from
the system.
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Quasi-classical MD simulations are executed to study H

dissociation from the Al−OH2 system. The fourth-order
Runge−Kutta integration method with a fixed step-size of
1.018 × 10−16 s is employed to integrate 24 partial differential
equations simultaneously. We investigate seven levels of
excitation, with the total internal energy varying from 2.8 to
4.0 eV. At each internal energy level, 500 sampled trajectories
are investigated. In each trajectory, the maximum MD
integration period is 5 ps. A trajectory is terminated when
the chemical reaction occurs. To determine the occurrence of
H dissociation, we monitor the O−H1 bond and O−H2 bonds
at every integration step to determine whether the chemical
reaction of interest takes place. That is, if one of the O−H
bonds is >1.6 Å, we consider that the reaction happens, and the
reaction time as well as structural configuration will be
recorded.

III. RESULTS AND DISCUSSION

Figure 4. Plot of number of O−H dissociation samples versus internal
1. Quality of the Fitted PES. As previously discussed, we energy. The number of reacting samples is in direct proportion to
finally obtain a database of 92 834 Al+OH2 configurations to internal energy.
construct the PES. The overall average absolute error (aae) and
rmse for all data points are reported as 0.0031 eV (0.30 kJ/ were more than one H2O molecules interacting with the
mol) and 0.0033 eV (0.32 kJ/mol), respectively. The ratio catalytic Al cluster.
between two statistical uncertainties is ∼1.06, which suggests At the internal energy of 2.8 eV (with 1.03 eV activation
that there are a minor number of bad-fitting data points and energy), O−H dissociation in 5 ps occurs in only 38 samples
their error distribution does not significantly affect fitting (out of 500, accounting for 7.6%). When we raise the total
accuracy. In Figure 3a, we see a large number of data points energy to 3.0 eV, the reaction probability now increases to
with small absolute fitting errors, which dominates the 10.6%. With the internal energy of 4.0 eV (activation energy =
distribution plot. In fact, if we instead examine the distribution 2.23 eV), the number of reacting samples increases to 151
of fitting error, the plot would turn out to be a Gaussian-like (30.2%). To facilitate comparisons with experimental data, we
distribution. As obviously seen in Figure 3b, NN-predicted estimate the effective temperature with respect to each
energies are in very good agreement with the calculated ab excitation level. Because our MD simulations involve mode-
initio energies. It is shown clearly that most dots reside on the specific excitations, we can assume that the excitation energy
45° line. Figure 3c shows that the rmse of the training, acting on each vibrational mode (out of six modes in total)
validation, and independent testing sets drop consistently possesses a Boltzmann distribution and equals kBTeff. Adopting
during the training process. At the end of the training process, such an assumption, the effective temperature can be estimated
the rmse values of those three sets are 0.0036, 0.0033, and as shown in Table 4 (varying from 1992 to 4313 K). It should
0.0034 eV, respectively. Therefore, we can conclude that the
NN method results in an excellent fitting accuracy for the Table 4. Number of Reaction Samples Observed in 500
reactive PES describing O−H dissociation in the complex of Samples
aluminum and water.
2. Molecular Dynamics of the O−H bond Dissociation. internal excitation temperature number of percentage
energy (eV) energy (eV) (K) samples (%)
After investigating 500 samples for each internal energy, we
observe that the number of chemical reactions (O−H 2.80 1.03 1992 38 7.6
dissociations) is proportional to the level of internal energy. 3.00 1.23 2379 53 10.6
As illustrated in Figure 4, a linear relationship is established 3.20 1.43 2766 81 16.2
between number of reactions and internal energy. Assuming 3.40 1.63 3153 95 19.0
3.60 1.83 3539 109 21.8
that this linear behavior holds at all levels of internal energy, the
3.80 2.03 3926 131 26.2
minimum reactive energy may be determined. By interpolating
4.00 2.23 4313 151 30.2
the linear function, we find that 2.39 eV is the bottom line for
H dissociation on the constructed PES. In other words, an
excitation energy of 0.62 eV is the minimum requirement to be noted that the rotations are eliminated before executing MD
activate the reaction. Recall that in a previous work Sharipov et trajectories. For convenience, we summarize numbers of
al.8 suggested that the barrier for Al−OH2 to transform to the reaction samples and reaction probability values at all
trans conformation was 11.8 kJ/mol (0.12 eV). In the investigated energy levels in Table 4. Besides, the average
investigation of catalytic activity of different Aln clusters using time needed for reactivity at internal energies of 2.8 to 4.0 eV
DFT calculations, Liu et al.17 suggested the activation barrier to varies in a large range (from 0.082 to 0.909 ps) while the
fall in the range of 0.83 to 2.12 eV, which is higher than the average potential energy varies from 2.25 to 2.67 eV. The
activation barrier reported herein (0.62 eV). In another study, reaction time at 2.8 eV is very long in comparison with that at
Ohmura et al.52 considered the activity of Al in an aqueous 4.0 eV. At the highest investigated energy level, the chemical
environment, and the barrier for H dissociation was reported to reaction occurs in 151 samples after 1.5 ps, while it almost takes
be 0.42 eV if only one H2O molecule was involved in the the entire period of 5 ps for several samples to react at the 2.8
reaction. The barrier might drop to 0.20 to 0.30 eV if there eV.
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For the H dissociation to occur, the process usually
undergoes two stages: the combination of Al−O with
rearrangement to cis/trans configuration and the following
cleavage of one H atom. In addition to the overall process of H
dissociation, we also examine slow rate-determining step (Al−
O combination) by monitoring the Al−O bond in each
trajectory. If the bond becomes shorter than 1.83 Å (according
to the saddle point presented in Figure 1d), we conclude there
is an Al−O combination. Subsequently, we perform a statistical
analysis to examine if the Al−O combination and the overall H
dissociation are of first-order type. As shown in Figure 5,
Figure 5. Decaying plots of O−H dissociation samples with respect to
time at different internal energy levels.
because of nonlinearity of the logarithm decaying curves, those
two processes are concluded not to be first-order reactions.
This is due to the direct involvement of Al, O, and H in the
Figure 6. (a) Plot of potential energy versus time. (b) Plot of Al−H1 and Al−H2 distances versus time. (c) Snapshots of AlOH2 configurations
during a trajectory resulting in O−H bond cleavage. The internal energy of this process is 2.8 eV.
G DOI: 10.1021/acs.jpca.5b09497
Article
elementary rate-determining process. That is, when the Al−O
combination takes place, one of the H atoms interacts with Al
at the same time, followed by the structural rearrangement to
the cis/trans configuration.
At the low excitation energy levels (1.03 to 1.63 eV), the rate
of overall H dissociation process seems to be lower than the
rate of the Al−O combination step. This implies the fact that H
dissociation actually relies on the rate-determining step. Unlike
the low excitation energy cases, at the high excitation energy
levels (1.83 to 2.23 eV), the rate of H dissociation is slightly
higher than the Al−O combination. In some rare cases, H
dissociation can even occur without the full combination of Al
and O to establish the cis/trans configuration.
In the following discussion, we will show that the O−H
dissociation dynamics in the Al−OH2 system is directly
correlated to the strength of Al−O bond and change in Al−
O bond length. Initially, aluminum gets attached to water and
the Al−OH2 complex is formed when Al moves toward O. In
the equilibrium structure of Al−OH2, we can regard the Al−O
linkage as a weak bond. There are two pieces of evidence of this
conclusion. First, the bond is too long (with a distance of 2.23
Å) to be considered as a covalent bond. Second, according to
our vibrational mode analysis, two vibrations associated with Al
movements have low energies (129 and 214 cm−1). For the
breaking of one O−H bond, H should be pushed away from
the O atom, while at the same time, Al should approach closer
to O until the O−H bond reaches 1.6 Å (considered as the
dissociation distance). As the O−H bond is extended, the H
atom more or less behaves like a radical and becomes active. As
a result, it highly prefers to conjoin with the Al−OH complex
and form the H−Al−OH configuration (in either cis or trans
conformation). At this point, the internal energy would play a
decisive role in determining the final product. In the case of low
internal energy, the H−Al−OH configuration remains stable
for a period of time. If the internal energy is high enough, the
Al−O bond shrinks and H is active enough to split off from the
complex. The residual O−H bond can even stretch and become
finally broken when the Al−O bond continues to shrink.
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The Journal of Physical Chemistry A
Figure 7. (a) Plot of potential energy versus time. (b) Plot of Al−H1 and Al−H2 distances versus time. (c) Snapshots of AlOH2 configurations
during a trajectory resulting in O−H bond cleavage. The internal energy of this process is 4.0 eV.
According to Sharipov et al., the possible pathway for hydrogen
production was Al + H2O → AlOH2 → HAlOH → AlOH + H
→ AlO + H2.8 Our study provides theoretical support for this
mechanism.
In Figures 6 and 7, we present illustrations for two different
chemical schemes at two levels of internal energy: 2.8 and 4.0
eV. In each case, the snapshots showing Al−OH2 evolution
toward O−H dissociation are illustrated. In addition, we
examine the change in potential energy profile and Al−H bond
length with respect to time. At 2.8 eV, the O−H bond vibrates
around its equilibrium position for a long period of time before
H can dissociate, while the Al−H does not decrease
significantly after 1 ps. The Al−OH2 complex seems to be
rather stable because we are still able to observe the O−H
bonds until 0.8 ps; however, at 1.16 ps, the cis configuration is
established and the H dissociation takes place very rapidly
(only 0.03 ps after the event). In the plot of Al−H bonds
(Figure 6b), there is evidence that such a distance is shortened
but suddenly becomes prolonged. This is a clear evidence of H
dissociation from Al.
In the sample with 4.0 eV internal energy presented in Figure
7 (activation energy = 2.23 eV), the O−H bond seems to
vibrate stronger, and the H atom can escape more easily. In the
snapshots, neither the cis nor trans configuration can be found,
and H dissociation occurs due to the fact that the O−H bond
breaks after a simple process of Al attachment. At the internal
energy of 4.0 eV, Al behaves like a bullet; thus, geometric
transformation takes place more rapidly. As a result, the
dissociation reaction happens easier and much faster in
comparison with the previous case. Again, like in Figure 6b,
we also observe in Figure 7b evidence showing that Al−H bond
is established and becomes immediately broken. In addition,
after the H dissociation occurs, the potential energy drops
significantly. Therefore, we can conclude that even though this
reaction requires high activation energy, it is exothermic and
the final product is more stable than the initial state.
H DOI: 10.1021/acs.jpca.5b09497
Article
IV. SUMMARY
In this study, we have investigated the O−H dissociation
dynamics from Al−OH2 on a PES constructed by NN fitting of
ab initio data. Reaction probability is computed at various levels
of vibrational excitation. To construct the ab initio database, we
employ a dynamic approach, in which configurations are
iteratively sampled using MD trajectories. The electronic
structure calculations are executed at the MP2 level of theory
with the 6-311G (3df, 2p) basis set. A two-layer feed-forward
NN with 60 neurons in the hidden layer is utilized to perform
numerical fit for MP2 energies. In total, 92 834 data points have
been collected to cover the reaction region in the 6D
hyperspace. The rmse values for the training and testing sets
are, respectively, reported as 0.0036 and 0.0034 eV, which
reveals excellent fitting accuracy.
In MD simulations, the fourth-order Runge−Kutta method is
utilized to integrate the differential equations of motion for 5 ps
or until the H dissociation is identified. MD trajectories of Al−
OH2 system are executed at seven levels of internal energy
(from 2.8 to 4.0 eV) to calculate the probability of O−H bond
dissociations. We also monitor dissociation time as well as
chemical reaction pathways. Our theoretical investigation
demonstrates that the O−H dissociation is primarily related
to the evolution of Al−O bond length. Such a chemical reaction
usually undergoes two complex stages: AlOH2 → HAlOH →
AlOH + H. We do, however, find that the direct departure of H
from AlOH2 is also available if the activation energy is high
enough. With 500 investigated samples for each internal energy,
we observe that, in general, the reaction relies heavily on the
combination of Al−O (from a weak bond to a covalent bond).
The number of reacting samples seems to be proportional to
internal energy. On the basis of this linear relationship, we
determine that a minimum internal energy of 2.39 eV is
required for the O−H dissociation. In other words, an
activation energy of 0.62 eV should be introduced to activate
O−H dissociations. At the lowest internal energy level in our
investigation (in particular, 2.8 eV), the O−H bond length and
potential energy seem to fluctuate and the O−H dissociation
J. Phys. Chem. A XXXX, XXX, XXX−XXX
The Journal of Physical Chemistry A
needs a longer period to happen. When the internal energy is as
high as 4.0 eV, the chemical reaction occurs more rapidly.
Overall, the portrait of single-Al-atom catalysis drawn in this
study seems to be realistic for hydrogen production because of
reasonable activation energy (0.62 eV). Although the results
obtained for the simple model are promising, further
computational studies are necessary to clarify how adding
more Al atoms and aqueous environment can affect the
energetics of the dissociation process.
■ AUTHOR INFORMATION
Corresponding Author
*E-mail: leminhhung@tdt.edu.vn; hung.m.le@hotmail.com.
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
We thank the University of Science, Vietnam National
University and the Institute for Materials Research, Tohoku
University for their computing supports. This work is funded
by VNU under grant HS-2014-18-01.
■
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