Abstract
First principles pseudopotential density functional calculations have been performed to investigate the reactivity of O2 on ideal and defected surface of rutile TiO2 (110). All ionic positions are allowed to relax on slab geometry with periodic boundary conditions. The results reveal that both the molecular and dissociated adsorption of O2 is most favourable on a defective surface in the presence of titanium vacancy and a substantial change in surface relaxation was observed. This remarkable surface ionic displacement and titanium vacancy induced acceptor-like environment favoured in stable adsorption of oxygen for both molecular and dissociated states. The least favourable adsorption or no adsorption of O2 is observed on an ideal surface.
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References
1.
Guillemot
F.
,
Portè
M. C.
,
Labrugere
C.
andCh. Baquey : J. Colloid Interf Set , 2002 , 255 , 75 .
2.
Zhang
F.
,
Liu
X.
,
Mao
Y.
,
Huang
N.
,
Chen
Y.
,
Zheng
Z.
,
Zhou
Z.
,
Chen
A.
and
Jiang
Z.
Surf Coat. Technol. , 1998 , 103 –104 , 146 –150 .
3.
Henry
C. R.
: Surf Set Rep. , 1998 , 31 , 235 .
4.
Valden
M.
,
Lai
X.
and
Goodman
D. W.
Science , 1998 , 281 , 1647 .
5.
Campbell
C. T.
,
Parker
S. C.
and
Starr
D. E.
Science , 2002 , 298 , 811 .
6.
Linsebigler
A. L.
,
Lu
G.
and
Yates
J. T.
Chem. Rev. , 1995 , 95 , 735 .
7.
Huusko
J.
,
Lantto
V.
and
Tovela
H.
Sens. Actuators B , 1993 , 16B , 245 .
8.
Rothschild
A.
,
Edelman
F.
,
Komem
Y.
and
Cosandey
F.
Sens. Actuators B , 2000 , 67B , 282 –289 .
9.
Grant
F. A.
: Rev. Mod Phys. , 1959 , 31 , 646 .
10.
Marucco
J.-F.
,
Gautron
J.
and
Lemasson
P.
J. Phys. Chem. Solids , 1981 , 42 , 363 .
11.
Kofstad
P.
: J. Less-Common Met. , 1967 , 13 , 635 .
12.
Nowotny
J.
,
Radecka
M.
and
Rekas
M.
J. Phys. Chem. Solids , 1977 , 58 , 927 .
13.
Kofstad
P.
: J. Phys. Chem. Solids , 1962 , 23 , 1579 .
14.
Balachandran
U.
and
Eror
N. G.
J. Mater. Sci. , 1988 , 23 , 2676 .
15.
Blanchin
M. G.
,
Faisant
P.
,
Picard
C.
,
Ezzo
M.
and
Fontaine
G.
Phys. Status Solidi , 1980 , 60a , 357 .
16.
Marucco
J. F.
,
Poumellec
B.
,
Gautron
J.
and
Lemasson
P.
J. Phys. Chem. Solids , 1985 , 46 , 709 .
17.
Barbanel
V. I.
,
Bogomolov
V. N.
,
Borodin
S. A.
and
Budarina
S. I.
Fiz. Tvierd Tiela (Russ. Solid State Phys .), 1969 , 11 , 534 .
18.
Diebold
U.
: Surf Sci. Rep. , 2003 , 48 , 53 –229 .
19.
Fox
M. A.
and
Dulay
M. T.
Chem. Rev. , 1993 , 93 , 341 .
20.
Mills
A.
,
Davies
R. H.
and
Worsley
D.
Chem. Soc. Rev. , 1993 , 22 , 417 .
21.
Perdew
J. P.
and
Wang
Y.
Phys. Rev. B , 1992 , 45B , 13244 .
22.
Perdew
J. P.
,
Chevary
J. A.
,
Vosko
S. H.
,
Jackson
K. A.
,
Pederson
M. R.
,
Singh
D. J.
and
Fiolhais
C.
Phys. Rev. B , 1992 , 46B , 6671 .
23.
Vanderbilt
D.
: Phys. Rev. B , 1990 , 41B , 7892 .
24.
Segall
M. D.
,
Lindan
P. L. D.
,
Probert
M. J.
,
Pickard
C. J.
,
Hasnip
P. J.
,
Clark
S. J.
and
Payne
M. C.
J. Phys.: Condens. Mat. , 2002 , 14 , 2717 .
25.
Payne
M. C.
,
Teter
M. P.
,
Allan
D. C.
,
Arias
T. A.
and
Joannopoulos
J. D.
Rev. Mod. Phys. , 1992 , 64 , 1045 .
26.
Clarke
L. J.
,
Stich
I.
and
Payne
M. C.
Comput. Phys. Commun. , 1992 , 72 , 14 .
27.
Monkhorst
H. J.
and
Pack
J. D.
Phys. Rev. B , 1976 , 13B , 5188 .
28.
Fischer
T. H.
and
Almlof
J.
J. Phys. Chem. , 1992 , 96 , 9768 .
29.
Lindsay
R.
,
Wander
A.
,
Ernst
A.
,
Montanan
B.
,
Thornton
G.
and
Harrison
N. M.
Phy. Rev. Lett. , 2005 , 94 , 246102 .
30.
Charlton
G.
,
Howes
P. B.
,
Nicklin
C. L.
,
Steadman
P.
,
Taylor
J. S. G.
,
Muryn
C. A.
,
Harte
S. P.
,
Mercer
J.
,
McGrath
R.
,
Norman
D.
,
Turner
T. S.
and
Thornton
G.
Phys. Rev. Lett. , 1997 , 78 , 495 .
31.
Ramamoorthy
M.
,
Vanderbilt
D.
and
King-Smith
R. D.
Phys. Rev. B , 1994 , 49B , 16721 .
32.
Ramamoorthy
M.
,
King-Smith
R. D.
and
Vanderbilt
D.
Phys. Rev. B , 1994 , 49B , 7709 .
33.
Oviedo
J.
,
Miguel
M. A. S.
and
Sanz
J. F.
J. Chem. Phys. , 2004 , 121 , 7427 .
34.
Wang
Y.
,
Pillay
D.
and
Hwang
G. S.
Phys. Rev. B , 2004 , 70B , 193410 .
35.
de Lara-Castells
M. P.
and
Krause
J. L.
J. Chem. Phys. , 2001 , 115 , 4798 .
36.
Fischer
S.
,
Munz
A. W.
,
Schierbaum
K.-D.
and
Gopel
W.
Surf Set , 1995 , 337 , 17 .