The electronic structure of BiVO4 has been studied by x-ray photoelectron, x-ray absorption, and x-ray emission spectroscopies, in comparison with density functional theory calculations. Our results confirm both the direct band gap of 2.48 eV and that the Bi6s electrons hybridize with O2p to form antibonding “lone pair” states at the top of the valence band. The results highlight the suitability of combining s2 and d0 cations to produce photoactive ternary oxides.

1.
A.
Fujishima
and
K.
Honda
,
Nature (London)
238
,
37
(
1972
).
2.
A.
Kudo
,
K.
Omori
, and
H.
Katol
,
J. Am. Chem. Soc.
121
,
11459
(
1999
).
3.
A.
Kudo
,
MRS Bull.
36
,
37
(
2011
).
4.
Z.
Yi
,
J.
Ye
,
N.
Kikugawa
,
T.
Kako
,
S.
Ouyang
,
H.
Stuart-Williams
,
H.
Yang
,
J.
Cao
,
W.
Luo
,
Z.
Li
,
Y.
Liu
, and
R. L.
Withers
,
Nature Mater.
9
,
559
(
2010
).
5.
A.
Walsh
,
Y.
Yan
,
M. N.
Huda
,
M. M.
Al-Jassim
, and
S. -H.
Wei
,
Chem. Mater.
21
,
547
(
2009
).
6.
D. J.
Payne
,
R. G.
Egdell
,
A.
Walsh
,
G. W.
Watson
,
J.
Guo
,
P. -A.
Glans
,
T.
Learmonth
, and
K. E.
Smith
,
Phys. Rev. Lett.
96
,
157403
(
2006
).
7.
A.
Walsh
,
J. L. F. D.
Silva
,
S. -H.
Wei
,
C.
Korber
,
A.
Klein
,
L. F. J.
Piper
,
A.
DeMasi
,
K. E.
Smith
,
G.
Panaccione
,
P.
Torelli
,
D. J.
Payne
,
A.
Bourlange
, and
R. G.
Egdell
,
Phys. Rev. Lett.
100
,
167402
(
2008
).
8.
L. F. J.
Piper
,
A.
DeMasi
,
S. W.
Cho
,
A. R. H.
Preston
,
J.
Laverock
,
K. E.
Smith
,
K. G.
West
,
J. W.
Lu
, and
S. A.
Wolf
,
Phys. Rev. B
82
,
235103
(
2010
).
9.
H.
Luo
,
A. H.
Mueller
,
T. M.
McCleskey
,
A. K.
Burrell
,
E.
Bauer
, and
Q. X.
Jia
,
J. Phys. Chem. C
112
,
6099
(
2008
).
10.
See supplementary material at http://dx.doi.org/10.1063/1.3593012 for a full description of these experimental techniques.
11.
P.
Hohenberg
and
W.
Kohn
,
Phys. Rev.
136
,
B864
(
1964
).
12.
W.
Kohn
and
L. J.
Sham
,
Phys. Rev.
140
,
A1133
(
1965
).
13.
G.
Kresse
and
J.
Furthmuller
,
Comput. Mater. Sci.
6
,
15
(
1996
).
14.
G.
Kresse
and
J.
Furthmuller
,
Phys. Rev. B
54
,
11169
(
1996
).
15.
M. C.
Payne
,
M. P.
Teter
,
D. C.
Allan
,
T. A.
Arias
, and
J. D.
Joannopoulos
,
Rev. Mod. Phys.
64
,
1045
(
1992
).
16.
J. P.
Perdew
,
K.
Burke
, and
M.
Ernzerhof
,
Phys. Rev. Lett.
77
,
3865
(
1996
).
17.
A. R. H.
Preston
,
B. J.
Ruck
,
L. F. J.
Piper
,
A.
DeMasi
,
K. E.
Smith
,
A.
Schleife
,
F.
Fuchs
,
F.
Bechstedt
,
J.
Chai
, and
S. M.
Durbin
,
Phys. Rev. B
78
,
155114
(
2008
).
18.
W. -J.
Yin
,
S. -H.
Wei
,
M. M.
Al-Jassim
,
J.
Turner
, and
Y.
Yan
,
Phys. Rev. B
83
,
155102
(
2011
).
19.
O. Y.
Khyzhun
,
T.
Strunskus
,
W.
Grunert
, and
C.
Woll
,
J. Electron Spectrosc. Relat. Phenom.
149
,
45
(
2005
).

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