DFT+U Study of Rutile

TiO2 with VO clusters

and Methanol
Dallon Penney, Henrik Kristofferson, Jeremy Robins
DFT+U Study of VO on TiO2 slab
• Three conformers of VO on TiO2 were studied.
• The most stable VO configuration was used to study methanol
adsorption and dissociation.
• Vanadium would donate 1 electron to a third row Titanium atom
which was previously found to be the most stable configuration. The
Ti3+ was monitored on each calculation to ensure it did not move.
• Methanol binding energies were calculated.
3 VO
Conformers
Titanium Vanadium

and their Oxygen Vanadyl

Oxygen
Energies
0 eV +1.19 eV +1.11 eV
Ti3+ and Spin States
• The vanadium would donate 1 electron to
TiO2, which would then migrate to the 3rd
row. Previous work showed this is the most
stable place for the polaron. This was
monitored on subsequent calculations.
3rd row Ti3+, reduced • Because V has an odd number of electrons
by V on surface. (23), we set the magnetic moment to
either 1 or 3 (triplet on VO (2 aligned
electrons) + a doublet on Ti (one
electron)). We found that the MAGMOM=1
setting to be the most stable of the two.
The spins on Ti3+ and V don’t interact very
strongly, so the energy difference is small.
Density of States for Most stable VO
Configuration
Ninterval = ρenergy(E) dE
where ρenergy(E) is a function that when
multiplied by an interval of energy dE,
provides the carrier density Ninterval of
available states in that energy range. ρenergy(E)
is the density of states function which is
calculated for each atom in the unit cell by
the program.
Density of States for Most stable VO
Configuration (Zoomed in)
Total

Ti3+ d spin up

Ti3+ d spin down

V d spin up

V d spin down
 Vanadium

Single Methanol on VO Study Vanadyl

Oxygen

Eadsorbtion = -1.73 eV Methanol

Oxygen

0 eV +0.5 eV +1.1 eV
Single Methanol on Bare TiO2
• A single methanol has a
binding energy on bare
TiO2 of -1.26 eV.
Adsorbed Methoxide Hydrogen
Placement Study Vanadium

0 eV +0.12 eV +0.18 eV Vanadyl

Oxygen

Methanol
Oxygen

+0.38 eV +0.19 eV

Edissociation = -0.76 eV
 Vanadium

Adsorption of 2 nd
Methanol Study Vanadyl
Oxygen

Methanol
Oxygen
+0.06 eV +1.7 eV 0 eV

Eadsorption(2nd) = -1.33 eV
2 Adsorbed Methoxide Hydrogen Placement Study
  49 eV
+0.   32eV
+0.   62 eV
+0.   35 eV
+0.

  .25 eV
+0   37 eV
+0. 0  eV

Vanadium

Vanadyl
Oxygen

Methanol
Oxygen
3 Adsorbed Methoxide Hydrogen Placement Study
0  eV +0.92
  eV   .51 eV
+0 +0.58
  eV

Vanadium

Vanadyl
Oxygen

Methanol
Oxygen
Nudged Elastic Band Method
Method for finding saddle points and minimum energy
pathways in the reaction landscape. Several images are
used as points along the reaction pathway. VASP takes the
highest energy image and maximizes the forces along the
band, thus when it is converged one of the images will
have zero forces at the top of the saddle point.
Reaction 1: give methyl hydrogen to methoxide to form
formaldehyde and methanol

Energy (eV)

Path (Å)
 Energy (eV)

Path (Å)