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Application Note

B.

Structure and Bond Lengths in Titanium Dioxide


In addition to the lattice parameters, the rutile structure has an additional degree of freedom,
namely the position of the oxygen atom. This case study shows the simultaneous calculation of all
these structural degrees of freedom.

Outline of Approach
The computational procedure involves the following steps

Choose crystal structure of TiO2


Compute lattice parameters of TiC
Analyze results
1. Choose crystal structure

After starting MEDEA, select INFOMATICA from Tools in the MEDEA tool bar and select
Search in the INFOMATICA pull-down menu. Choose Require that Formula is TiO2 and
Require that Structural Completeness Complete and run the search.

Select ICSD.39166 and click on the tab Coordinates.

Copyright Materials Design, Inc. 2002-2008

Materials Design Application Note

Structure and Bond Lengths in Titanium Dioxide

The position of the oxygen atom is (x,x,0). The experimental value of x in the case of structure
ICSD.39166 is 0.30492. The parameter x can be changed without destroying the symmetry of
the rutile structure. The following calculation determines this structure by ab initio theory.
2. Change displayed bonds

The display of structure ICSD.39166 with the default criterion for bond lengths gives bonds
between neighboring Ti atoms (blue). This can be easily changed. Select EditEdit bonds
from the MEDEA tool bar. Set the Bond factor from 1.1 to 1.0 and Apply the change.
3. Compute structure with VASP

With the crystal structure of TiO 2 in the MEDEA window as the active window (dark blue top
bar), we now compute the lattice parameters and the internal parameters using VASP. From
Tools in the MEDEA menu bar, select VASP 4.6 and invoke the V ASP 4.6 graphical user
interface by selecting VASP 4.6Run from the MEDEA tool bar. From the first panel
(Calculation), select Structure Optimization as type of calculation, check
Relax atom positions, Allow cell volume to change, Allow cell shape to change.
This optimizes cell and atom positions without constraints. The calculations are performed
with the precision Accurate. All other parameters are left at their defaults.
Copyright Materials Design, Inc. 2002-2008

Materials Design Application Note

Structure and Bond Lengths in Titanium Dioxide

Analyze results
a. Inspection of Job.out file
After successful completion, the status reported by the JobServer is finished. By clicking on
the job number, a page is opened which lists the available output files. Click on Job.out to
view the summary, the original and optimized cell parameters are reported in a table
denoted Cell parameters:

In the present case of TiO2, the cell parameters computed with the generalized gradient
approximation (GGA) and PAW potentials as implemented in VASP give lattice parameters of
a=4.5959 and c=2.9558 , which are within 0.1 % of the experimental values.
Cell parameters:
Parameter

Original

change

Final

---------- ------------ ---------- ------------ ----a

4.593400

0.002504

4.595904

0.1

4.593400

0.002504

4.595904

0.1

2.957500 -0.001715

2.955785 -0.1

alpha

90.000000

0.000000

90.000000

0.0

beta

90.000000

0.000000

90.000000

0.0

gamma

90.000000

0.000000

90.000000

0.0

The fractional coordinates, i.e. the position of the atoms expressed in units of the lattice
parameters are
Fractional Coordinates:
Atom

Initial Coordinates

-----

-------- -------- --------

Final Coordinates
-------- -------- --------

Ti1

0.0000

0.0000

0.0000

0.0000

0.0000

0.0000

O1

0.3049

0.3049

0.0000

0.3038

0.3038

0.0000

The internal parameter for the oxygen atom changes from 0.3049 to 0.3038.
Copyright Materials Design, Inc. 2002-2008

Materials Design Application Note

Structure and Bond Lengths in Titanium Dioxide

b. Measuring computed bond distances


Choose FileOpen from the main M EDEA menu bar. Select Previous Calculation from the
new dialog box. This brings up a list of available structures from previous calculations
performed via the JobServer. Select the desired structure, click Insert > > and confirm with
OK. The structure will appear in a new window in MEDEA. Move the cursor over a bond and
the bond length is displayed in the lower left of the MEDEA window. In the present case, one
of the two computed Ti-O bond lengths is 1.9519 , which is very close to the experimental
value of 1.9475 .

experimental

Copyright Materials Design, Inc. 2002-2008

computed

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