Computational Materials Science 74 (2013) 33–39

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Computational Materials Science

journal homepage: www.elsevier.com/locate/commatsci

Density functional theory investigations of bismuth vanadate: Effect

of hybrid functionals
Nitin Wadnerkar a,⇑, Niall J. English a,b,⇑
a
The SFI Strategic Research Cluster in Solar Energy Conversion, School of Chemical and Bioprocess Engineering, Belfield, Dublin 4, Ireland
b
Centre for Synthesis and Chemical Biology, University College Dublin, Belfield, Dublin 4, Ireland

a r t i c l e i n f o a b s t r a c t

Article history: Hybrid density functional theory (DFT) calculations were performed on the monoclinic clinobisvanite
Received 7 December 2012 polymorph of bismuth vanadate (BiVO4), which has piqued experimental and theoretical interest in
Received in revised form 1 March 2013 recent years due to its photo-active nature. In particular, the effect of using PBEsol and HSE06–PBEsol
Accepted 2 March 2013
functional, as corrected for the solid state, is gauged upon the predictive performance for electronic struc-
Available online 9 April 2013
ture, band gap and optical properties. It was found that HSEsol-type functionals offer better predictive
performance than PBEsol with respect to experimental data, although PBEsol performs comparatively
Keywords:
well for this system, despite its general well-known limitations. Nonetheless, appropriately-tuned
Bismuth vanadate
Density functional theory
HSE06–PBEsol hybrid functionals may provide an improved description of solids compared to PBE, PBEsol
Hybrid DFT and HSE06. Although the ‘standard’ proportion of exact exchange for HSEsol (25%) seems to provide a rel-
Electronic structure atively accurate band gap vis-à-vis experiment, a smaller proportion (circa 10%) achieves quantitative
Optical properties agreement in this respect; in addition, the prediction of the lattice constants and band gaps is improved
substantially. For HSE06–PBEsol, analysis of the density of states analysis showed that the conduction-
band minimum (CBM) and valence-band maximum (VBM) position shift upwards and downwards,
respectively, thus widening the band gap, in better agreement with experimental results. It was found
that clinobisvanite is an indirect (albeit closer to a direct) band-gap semiconductor, and the optical prop-
erties were investigated, including the effect of varying the proportion of exact exchange thereon.
Ó 2013 Elsevier B.V. All rights reserved.

1. Introduction photo-decomposition of organic pollutants [20] compared to the

Bismuth vanadate (BiVO4) displays various interesting and
desirable physical properties, such as ionic conductivity [1] and
ferro-elasticity [2]; it is also non-toxic [3]. In recent years, how-
ever, bismuth vanadate has been recognised as a visible-light-dri-
ven photo-catalyst [3–9]. In particular, its low band-gap (circa
2.4 eV), adequate band-edge alignment vis-à-vis water redox
potentials and good photon-to-current conversion efficiencies ren-
der it a natural choice to rival other potentially suitable solar-en-
ergy materials [10,11]. Various crystalline polymorphs of BiVO4
are known, i.e., orthorhombic pucherite, tetragonal dreyerite and
monoclinic scheelite (also known as ‘clinobisvanite’ [12]) have
been prepared to study their visible light response. Among these,
the monoclinic scheelite, or clinobisvanite, polymorph has been re-
ported to show higher photocatalytic activity for O2 evolution or
⇑ Corresponding authors. Address: The SFI Strategic Research Cluster in Solar
Energy Conversion, School of Chemical and Bioprocess Engineering, Belfield, Dublin
4, Ireland. Tel.: +353 1 7161646; fax: +353 1 7161177 (N.J. English), tel.: +353 1
7161866 (N. Wadnerkar).
E-mail addresses: wadnerkar_nitin@yahoo.com (N. Wadnerkar), niall.english@
ucd.ie (N.J. English).
other two [13–19].
The recent high-quality experimental results of Luo et al. [21],
Dunkle et al. [5], Castillo et al. [6], Yin et al. [10], Garcia Perez
et al. [9] highlight photo-electrochemical (PEC)-induced oxidation
under visible-light irradiation represent a challenging test for mod-
ern electronic-structure ab initio methods to probe, in an effort to
enhance our understanding of the photo-electronic properties of
BiVO4. Indeed, the use of doping in BiVO4 to ‘engineer’ band-gap
properties may constitute a possible fruitful avenue of research
[22,23], but a fundamental understanding of the electronic struc-
ture and optical properties of BiVO4 would add significant insight
to inform these activities. An accurate, detailed understanding
has remained somewhat elusive for the most photo-active phase,
clinobisvanite, which adopts the I/2b space group [12]. However,
Walsh et al. [24], Yin et al. [25], and Zhao et al. [26,27], have made
seminal progress towards this goal in applying Perdew–Burke–
Ernzerhof (PBE)-level [28] density functional theory (DFT) calcula-
tions to probe the electronic structure of clinobisvanite-BiVO4. The
role of doping by transition metals [26] and optical properties were
studied [27] by Zhao et al., with the conclusion that clinobisvanite-
BiVO4 shows promise as a photocatalytic material. A direct, under-
estimated band gap of 2.16 eV between the valence band (VB) and

0927-0256/$ - see front matter Ó 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.commatsci.2013.03.015
34 N. Wadnerkar, N.J. English / Computational Materials Science 74 (2013) 33–39
conduction band (CB) edge composed of O 2p and V 3d, respec-
tively has been reported using the PBE approach [24,25], with
speculation that coupling between V 3d, O 2p and Bi 6p reduces
the CB edge further, so as to retain a direct band gap. However,
UV–vis spectra suggest that BiVO4 has a dipole-allowed direct band
gap [11,29], which would contradict the findings of Walsh et al.
[24] and Yin et al. [25] of a VB edge which is primarily s in charac-
ter, with a direct band gap. Clearly, although very promising
PBE-level DFT modelling has added to our understanding of the
electronic structure and properties of BiVO4, the application of
more accurate hybrid functionals, tailored specifically to the solid
state, may indeed be necessary to arrive at a more definitive
picture of BiVO4’s photo-excited properties.
To this end, in this study, we seek to refine the DFT description
of BiVO4. The Kohn–Sham formulation of DFT is the most popular
electronic structure method, which provides an efficient method
for evaluation of materials properties [30]. Although, in principle,
DFT yields a good description of ground-state properties, practical
applications of DFT are based on approximations for the so-called
exchange-correlation potential. Possessing the exact exchange-
correlation potential means that the many-body problem would
be solved exactly, this is clearly not feasible in solids. It is well-
known that the mean-field-type one-particle description of the
electronic structure within the standard local density (LDA) or gen-
eralised gradient (GGA) approximations to DFT is incapable to cor-
rectly describe exchange and correlation effects in metal oxides,
resulting in under-prediction of band gaps and magnetic moments,
e.g. 2.16 eV for PBE-level BiVO4 relative to an experimental result
of circa 2.4 eV [13–19]. Recently, PBEsol was designed specifically
to improve GGA description of solids [31]. In addition, several
forms of hybrid method have been proposed to date and they differ
on how the exact exchange energy is mixed in the energy func-
tional, and prominent amongst these is the Heyd–Scuseria–Ernzer-
hof (HSE06) hybrid functional [32–34]. With hybrid functionals,
e.g., HSE06, there is often better agreement with experiment for
bulk lattice parameters for a wide class of materials relative to
GGA [32–34]. In addition, these functionals yield generally, inter
alia, much improved band gaps, electronic structure, and dielectric
and optical properties for extended systems vis-à-vis GGA (e.g., cf.
Refs. [32–34]). The underestimation of band gap with DFT has been
discussed by many researchers but not analysed to improve it to
date, especially for BiVO4 system. Recently, Zhao et al. discussed
the use of the ‘scissor-operator’ to recover the band gap [26]; this
is one possible route which, although perhaps alleviating the un-
der-estimation of band gap, does not address per se an improved
descriptions of electronic structure or other properties.
Therefore, in the present study, we apply hybrid DFT towards
realising a more accurate description of band gap, treatment of
electronic structure and dielectric and optical properties necessary
to obtain a more refined appreciation of the subtleties of clin-
obisvanite BiVO4’s electronic properties, in view of our interest in
it as a potential photo-catalyst. More specifically, we provide a de-
tailed comparison of various proportions of exact exchange in hy-
brid DFT for properties with respect to available experimental data
for BiVO4.
2. Methodology
Three-dimensional periodic spin-polarised density functional
theory (DFT) calculations were performed using the HSE06 hybrid
functional [32–34], as implemented in the Vienna ab initio Simula-
tion Package (VASP) code (v5.2.11) [35,36], using projector aug-
mented wave (PAW) pseudopotentials. The exchange-correlation
potential is divided into short-and long-range parts, and Hartree-
Fock (HF) exchange-correlation is mixed with PBEsol
exchange-correlation, as adjusted for solids [32] in the short-range
part. PBEsol was used due to its superior geometry prediction vis-
à-vis PBE exchange-correlation in solids [28,31], leading to more
accurate Born–Oppenheimer forces acting on the electronic wave-
functions, providing the best possible estimation of electronic
properties. To avoid the expensive calculation of long-range HF ex-
change, this term is replaced by long-range PBEsol exchange, as
shown in following equation:
HF;sr;l l l
EHSE
xc ¼ aEx þ ð1  aÞEPBE;sr;
x þ EPBEsol;lr;
x þ EPBEsol
c ð1Þ
where (sr) and (lr) refer to the short- and long-range parts of the
respective exchange interactions, and a denotes the proportional
contribution of exact exchange (typically 25% [32–34]). Control of
the range separation may be achieved by varying the Coulomb ker-
nel, typically between 0.2 and 0.3 Å1. We have used l = 0.2 Å1 for
HSE06; the exact exchange contribution of 25% (cf. Eq. (1)) was sug-
gested originally by Becke [37,38] by fits to atomisation energy data
of a large number of molecular species, and is reasonably applicable
in hybrid-DFT. Although exact-exchange contributions other than
25% can yield more accurate intrinsic band gaps (i.e., determined
from electronic structure), for instance, for specific materials, this
contribution has still been widely applicable and used for a wide
range of materials. In any event, this choice of parameters for
HSE06–PBEsol is identical to the recent work of Schimka et al.
[39], who have found that this works well for a range of solids,
and also of McDonnell et al. [40], both with an exact-exchange con-
tribution if 25%. However, one of the key goals of this study is to
‘tune’ the exact-exchange contribution parameter a in Eq. (1) so
as to result in better agreement of the band gap with experiment;
it is often the case that applications of HSE06 omit this helpful step.
Although the studied material contains Bi and V elements, the
GGA + U approach was not adopted in the present study, given
the underlying motivation to treat the electronic structure as accu-
rately as possible. The use of GGA + U allows for the (empirical)
correction of band gap, but is less than satisfactory for the compu-
tation of other optical properties or in capturing the subtleties of
electronic structure.
Bulk calculations were performed on a symmetric slab
(2  1  1) unit cells of monoclinic clinobisvanite BiVO4, resulting
in a supercell containing 48 atoms. The electronic wave function
was expanded in plane waves up to a cutoff energy of 520 eV and
a C-centered k-point mesh [41] of 8  8  8 was used for geometry
optimisation and electronic-structure calculations. Both the atomic
positions and cell parameters were optimised until residual forces
were below 0.01 eV/Å. Electronic occupancies were determined by
the tetrahedron method.
For studies of optical properties, the frequency-dependent dielec-
tric matrix has been determined following electronic ground-state
geometry optimisation. The inter-band contribution to the imagi-
nary part, e2(x), of the dielectric tensor e(x) was calculated by sum-
mation over empty states. The real part of the dielectric tensor, e1(x),
was obtained via the Kramers–Kronig transformation [42]. For other
optical functions, we focused on the real part of the optical conduc-
tivity, r1(x) = xe2/4p, the energy-loss function on a volumetric ba-
sis, e2 ðe21 þ e22 Þ1 , and for surfaces, e2 ½ðe1 þ 1Þ2 þ e22 Þ1 , and also the
absorption coefficient, I(x) = 2xk/c, where the extinction coefficient,
k ¼ ð1=2Þ1=2 ½ðe21 þ e22 Þ1=2  e1 1=2 . In addition, the inter-band transi-
tion strength, Jcv, which accounts for dipole selection rules for the
transition, is proportional to probability that the transition of an elec-
tron between the occupied valence band and the empty conduction
band with a given transition energy takes place; the related dielectric
m2 4p2 2
constant, e, is given by ee2 h2 E2 ðe2 þ ie1 Þ [43,44]. Here, me is the mass
of the electron, E is the photon energy and h is Plank’s constant. For
computational convenience, we consider only the real part of the in-
ter-band transition (Re Jcv).
 N. Wadnerkar, N.J. English / Computational Materials Science 74 (2013) 33–39
3. Results and discussion
The lattice parameters calculated by PBEsol and HSE06–PBEsol
are shown in Table 1, with comparison to experimentally deter-
mined results [45]. As can be seen from parameters quoted in Ta-
ble 1, HSE06–PBEsol results with 10% exact exchange (viz. a = 0.1
in Eq. (1)) show good agreement with those obtained experimen-
tally, with difference less than 0.15%. On the other hand, PBEsol re-
sults display a difference of 0.2%, which is still very good in
absolute terms.
3.1. DOS and band structure
By comparing the recently calculated PBE and HSE band gap of
metal oxides one could argue that a smaller portion of exact Fock
exchange should be included in the hybrid functional framework
in order to obtain a better agreement with experiments [24,26].
The mixing of 1=4 of exact exchange with 3=4 of DFT exchange leads
to larger band gap (3.1 eV) for monoclinic clinobisvanite BiVO4. A
reduced amount of exact exchange vis-à-vis 10% leads to quite sat-
isfactory prediction of the experimental band gap. The ion-pro-
jected valence electron densities of states (DOSs) using PBEsol
and HSE06–PBEsol (with 10% exact exchange) are plotted in
Fig. 1. In the present work, we make use of electrostatic potentials
contributed by electrons and ions in a system. When these are
averaged over a unit cell, the reference energy is zero because of
the charge neutrality condition. The charge density of PBEsol and
HSE06–PBEsol functionals were found to be almost the same. Thus,
electrostatic potentials can be used as a common reference for cal-
culating the shift of the band edges. Using the common reference,
we investigate the shift in the band edges. The position of the con-
duction band minimum (CBM) shift upwards by about 0.21 eV
using the HSE06–PBEsol functional with respect to PBEsol values.
Similarly, a shift is observed in the valence band maximum
(VBM) by about 0.18 eV (i.e., a downward shift). The shift in
CBM and VBM is very similar, and this rationalises the observed
widening of the band gap. In Fig. 2, the top of valence band is set
at zero. The key O 2p-based valence band is spread between 0
and 5/6.2 eV with PBEsol/HSE06–PBEsol functional. A peak
can be seen at 9.5 and 9.8 eV consisting of the majority of Bi
6s states using PBEsol and HSE06–PBEsol, respectively. From
Fig. 2, it can be seen clearly that the width of band gap differs with
different functionals. The conduction bands above 5 eV mainly
shows the characteristics of Bi 6p states which is not shown in
Fig. 1.
The calculated band structure along high-symmetry directions
of Brillouin zone is shown in Fig. 3. The minimum band gaps
(2.09 eV using PBEsol), indirect band gaps are obtained between
VBM and CBM. As can be seen, the direct band gaps are larger on
other k-points and relative to experimental band gap; similarly,
some recent studies have suggested this system has a direct band
gap [11,14,22,24,29]. But to avoid this possibly misleading direc-
tion, accurate band-gap calculations are necessary to ascertain
whether the band gap is direct or indirect. Our calculations with
Table 1
Equilibrium lattice parameters of monoclinic clinobisvanite BiVO4 (I/2b space group)
from experiment and DFT.
Experimenta PBEb PBEsol HSE06–PBEsol
a (Å) 5.195 5.108 5.186 5.190
b (Å) 11.701 11.522 11.642 11.681
c (Å) 5.092 5.108 5.056 5.073
b (°) 90.380 89.992 90.000 90.210
a
Swanson et al. [46].
b
Zhao et al. [26].
35
the HSE06–PBESol functional (using 10% exact exchange) reveals
a substantially improved estimation of the band gap (2.41 eV) with
respect to experimental findings and the relevant band structure
(cf. Fig. 2); the band structure of Fig. 2 also shows that there is
an indirect band gap between the VBM and CBM (albeit closer to
a direct band gap along high-symmetry k-points). This finding sup-
ports observed experimental UV–vis findings [11,29] (discussed in
Section 1).
3.2. Optical properties
It is well known that DFT underestimates the band gaps of
semiconductors and insulators [46] and the same feature has been
observed by Park et al. in their calculations [47]. Recently, Zhao
et al. [27] determined the band gap in for BiVO4 consistent with
experiment with use of the ‘scissor’-operator approach, and they
compared their investigated optical properties with the experi-
mental results of Li et al. [48] they found consistent results, like
for refractive-index functions. However, in the case of surfaces,
the validity of the scissors operator can be unsatisfied, since self-
energy corrections can be different for the surface and bulk states,
which experience different screening. This fact has been pointed
by Olivia et al. for GW calculations of GaAs (1 1 0) [49]. Taking
these factors into consideration, an alternative approach, based
on partial exact treatment of the exchange energy may well yield
a more reliable estimation of the optical band gap. The experimen-
tal band gap for BiVO4 (2.4–2.5 eV) [22] is comparably small. It
was found that a smaller amount (less than 25%) of exact ex-
change is sufficient to recover the correct experimental band gap
computationally. In addition, Zhao et al. [27] have described aniso-
tropic behaviour of monoclinic clinobisvanite BiVO4, and found
that visible light absorption arises mainly from the contribution
of polarisation directed along the a- and c-axes. We also observed
the same optical anisotropy in our calculations. In this work, we
have considered polarisation along the major contributory direc-
tions of the a- and c-axes, and averaged over these to evaluate
optical properties. The absorption spectra derived using PBEsol
and HSE06–PBEsol functionals are shown in Fig. 3. As shown in
the inset of Fig. 3, a linear relationship between (aE(x))2 and
E(x) indicates that monoclinic clinobisvanite BiVO4 would, at first
glance, exhibit behaviour suggestive of a direct band gap. The cal-
culated energy gaps of BiVO4 are around 2.09 eV and 2.41 eV,
using PBEsol and HSE06–PBEsol (with 10% exact exchange),
respectively. This finding is somewhat contradictory to our band
structure calculations shown in Fig. 2, but it also reveals that
band gap, although actually indirect (cf. Fig. 2), in agreement with
UV–vis findings, is also very close to exhibiting direct behaviour.
Overall, we found that absorption spectra obtained with the
HSE06–PBEsol functional are in better agreement with experiment
(both qualitative in that it captures the indirect nature of the band
gap, and also quantitative) than other recent studies of BiVO4 [24–
27], especially with the admixture of 10% exact exchange. This
emphasises the key advantage of hybrid DFT in conjunction with
PBEsol for extended solids, as pointed out by Schimka et al. [39].
The HSE06–PBEsol hybrid functional also performs significantly
better than semi-local PBEsol functional with respect to experi-
mental results for this system, although PBEsol performs reason-
ably well (as discussed earlier).
Reference to the lattice parameters in Table 1 shows that the
structure can be regarded as a slightly distorted tetragonal struc-
ture (I/2b space group). This kind of distortion does not occur in
tetragonal dreyerite structure, indicating the difference between
clinobisvanite and dreyerite BiVO4, which has been discussed
earlier by Zhao et al. [27]. For comparison, we also investigated
the index of refraction with PBEsol and HSE06–PBEsol (cf. Fig. 4)
and found that the HSE06–PBEsol method provides good agree-
36 N. Wadnerkar, N.J. English / Computational Materials Science 74 (2013) 33–39

Fig. 1. Ion-projected electronic density of states for BiVO4 using: (a) PBEsol and (b) HSE06–PBEsol (with 10% exact exchange). The highest occupied state is set to 0 eV (dashed
vertical line).

Fig. 2. Electronic band structure along high-symmetry k-points (L-M-A-C-Z-V). The highest occupied state is set to 0 eV.

ment with experiment and theory via the ‘scissor’-operator ap-
proach [27], suggesting that this hybrid method (HSE06–PBEsol)
is quite reasonable for such systems. In addition to these optical
properties, we investigated other optical properties which have
not yet been described in the literature with an accurate band
gap consistent with experiments. The behaviour of both surface
and bulk energy loss function as a function of photon energy is
illustrated in Fig. 5, denoted by Ls(x) and L(x), respectively. The
broad peaks are around 11 and 11.5 ev, using PBEsol and HSE06–
PBEsol (with 10% exact exchange), respectively in the L(x) spectra
in Fig. 5. These peaks are related to inter-band transitions from the
O 2p states to the V 3d state. We identified that the plasmon peak
lies at around 22 eV in the L(x) spectra. In addition, the featured
PBEsol peaks at around 13.5, 16, 19, and 28.5 eV in the real part
of the inter-band transition strength (Re Jcv) are attributable to
electronic transitions from O 2s energy levels to lower in the con-
duction band of bivo4, whereas the corresponding values for
HSE06–PBEsol occur at 14.2, 16.7, 20.4 and 29.5 eV, which is
broadly similar.
3.3. Photocatalytic properties
On the basis of results, we speculate that BiVO4 is an important
photocatalyst with its narrow band gap feature, although
 N. Wadnerkar, N.J. English / Computational Materials Science 74 (2013) 33–39 37

Fig. 3. Calculated absorption spectrum of BiVO4 summed over all possible direct valence-to-conduction band transitions using PBEsol and HSE06–PBEsol (with exact
exchange of 10% (HSE06–PBEsol-EX10), 15% (HSE06–PBEsol-EX15), and 25% (HSE06–PBEsol-EX25)). The inset plot of (aE(x))2 versus E(x) shows PBEsol (in red colour online)
and HSE06–PBEsol with 10% exact exchange (in green colour online). (For interpretation of the references to colour in this figure legend, the reader is referred to the web
version of this article.)

Fig. 4. Index of refraction ‘n’ of monoclinic clinobisvanite BiVO4 with PBEsol (red colour online) and HSE06–PBEsol (green colour online) with 10% exact exchange. (For
interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)

time-dependent DFT methods, non-adiabatic molecular dynamics
or Greens’ function methods would be required to probe further ex-
cited-state processes. Nonetheless, experimental data do show that
BiVO4 is a very promising photocatalytic material. In addition, the
observed optical anisotropy in monoclinic clinobisvanite BiVO4 in
this study, and others [27], plays a vital role in photocatalytic pro-
cess and helps to study the surface controlled fabrication of nano-
crystals or nanosheets; in recent studies, Zhang et al. showed a
preferred surface orientation (0 1 0) for enhanced photocatalytic
properties [50]. Overall, the optical properties results suggest more
enhanced visible-light absorption along direction of a- and c-axes,
and this is confirmed by recent experiments with the preparation
of controllable crystallographic facets (0 0 1) and (1 0 0) of BiVO4
[51].
38 N. Wadnerkar, N.J. English / Computational Materials Science 74 (2013) 33–39
Fig. 5. Calculated optical functions for BiVO4: (a) the real part of optical conductivity r1(x) (in 103 X1 cm1), (b) the bulk energy-loss function, L(x), (c) the surface energy-
loss function, Ls(x), and (d) the real part of the inter-band transition strength, Re (Jcv(x)). As in the inset plot of Fig. 3, shown here are PBEsol (in red colour online) and HSE06–
PBEsol with 10% exact exchange (in green colour online). (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this
article.)
4. Conclusions
Hybrid DFT calculations on the electronic structure and optical
properties of monoclinic clinobisvanite BiVO4, have been carried
out in this work using PAW pseudopotentials. Even though the
standard value of exact exchange (25%) in HSE seems to provide
a rather accurate band gap, clearly a smaller amount of exact ex-
change is necessary to obtain a better band gap. Despite all its well
known limitations when applied to the materials, PBE does not
seem to perform badly. But we believe that the HSE06–PBEsol hy-
brid functional provides an improved description of solids com-
pared to PBE, PBEsol and HSE06. Specifically, the prediction of
lattice constants and band gaps is much improved. Here, using
the hybrid HSE06–PBEsol functional with 10% exact exchange,
the density of states and band structure analysis of monoclinic
clinobisvanite BiVO4 showed that CBM and VBM position shift up-
wards and downwards by a margin, widening the band gap, which
is in better agreement with experimental results. It is found that
monoclinic clinobisvanite BiVO4 is an indirect (closer to direct)
band gap semiconductor, supporting recent experimental findings.
Acknowledgements
This work was supported by the Science Foundation Ireland
(SFI) Research Frontiers Programme (Ref. No. 10/RFP/MTR2868).
The authors thank Run Long, Sankha Ghosh, Kevin McDonnell, De-
nis Dowling and J.M.D. MacElroy for useful discussions, and Sci-
ence Foundation Ireland (SFI) and the Irish Centre for High End
Computing for the provision of computational resources, in addi-
tion to productive interactions with the SFI-funded Strategic Re-
search Cluster on Advanced Biomimetic Materials for Solar
Energy Transformation (Ref. No. 07/SRC/B1160).
References
[1] F. Abraham, M.F. Debreuille-Gresse, G. Mairesse, G. Nowogrocki, Solid State
Ionics 28 (1988) 529.
[2] T.L. Baker, K.T. Faber, D.W. Readey, J. Am. Chem. Soc. 74 (1991) 1619.
[3] D.N. Ke, T.Y. Peng, L. Ma, P. Cai, K. Dai, Inorg. Chem. 48 (2009) 4685.
[4] M. Shang, W.Z. Wang, S.M. Sun, J. Ren, L. Zhou, L. Zhang, J. Phys. Chem. C 113
(2009) 20228.
[5] S.S. Dunkle, R.J. Helmich, K.S. Suslick, J. Phys. Chem. C 113 (2009) 11980–
11983.
[6] N.C. Castillo, L. Ding, T. Graule, C. Pulgarin, J. Photochem. Photobiol. A: Chem.
216 (2010) 221.
[7] N.C. Castillo, A. Heel, T. Graule, C. Pulgarin, Appl. Catal. B: Environ. 95 (2010)
335.
[8] W. Yin, W. Wang, L. Zhou, S. Sun, L. Zhang, J. Hazard. Mater. 173 (2010) 194–
199.
[9] U.M. Garcia Perez, S. Sepulveda-Guzman, A. Martinez-de la Cruz, U. Ortiz
Mendez, J. Mol. Catal. A: Chem. 335 (2011) 169–175.
[10] H. Yin, Y. Sun, D. Shi, X. Wang, L. Wang, Int. J. Phys. Sci. 6 (2011) 4287.
[11] B. Zhou, J. Qu, X. Zhao, H. Liu, J. Environ. Sci. 23 (2011) 151.
[12] A.W. Sleight, H.Y. Chen, A. Ferretti, D.E. Cox, Meter. Res. Bull. 14 (1979) 1571.
[13] A. Kudo, K. Ueda, H. Kato, I. Mikami, Catal. Lett. 53 (1998) 229.
[14] A. Kudo, K. Omori, H. Kato, J. Am. Chem. Soc. 121 (1999) 11459.
[15] S. Tokunaga, H. Kato, A. Kudo, Chem. Mater. 13 (2001) 4624.
[16] S. Kothani, M. Koshiko, A. Kudo, K. Tokumura, Y. Ishigaki, A. Toriba, K.
Hayakawa, R. Nakagaki, Appl. Catal. B 46 (2003) 573.
[17] S. Kothani, J. Hiro, N. Yamamoto, A. Kudo, K. Tokumura, R. Nakagaki, Catal.
Commun. 6 (2005) 185.
[18] K. Sayama, A. Nomura, Z. Zou, R. Abe, Y. Abe, H. Arakawa, Chem. Commun.
2908 (2003).
[19] X. Zhang, Z. Ai, F. Jia, L. Zhang, X. Fan, Z. Zou, Mater. Chem. Phys. 103 (2007)
162.
[20] S. Tokunnagu, H. Kato, A. Kudo, Chem. Mater. 13 (2001) 4624.
[21] H. Luo, A.H. Mueller, T.M. McClesky, A.K. Burrell, E. Bauer, Q.X. Jia, J. Phys.
Chem. C 112 (2008) 6099.
[22] K. Sayama, A. Nomura, T. Arai, T. Sugita, R. Abe, M. Yanagida, T. Oi, Y. Iwasaki, Y.
Abe, H. Sugihara, J. Phys. Chem. B 110 (2006) 11352.
[23] W. Yao, H. Iwai, J. Ye, Dalton Trans. 11 (2008) 1426.
[24] A. Walsh, Y. Yan, M.N. Huda, M.M. Al-Jassim, S.-H. Wei, Chem. Mater. 21 (2009)
547.
[25] W.J. Yin, S.H. Wei, M.M. Al-Jassim, J. Turner, Y. Yan, Phys. Rev. B 83 (2011)
155102.
[26] Z. Zhao, W. Luo, Z. Li, Z. Zou, Phys. Lett. A 374 (2010) 4919.
 N. Wadnerkar, N.J. English / Computational Materials Science 74 (2013) 33–39
[27] Z. Zhao, Z. Li, Z. Zhou, Phys. Chem. Chem. Phys. 13 (2011) 4746.
[28] J.P. Perdew, K. Burke, M. Ernzerhof, Phys. Rev. Lett. 77 (1996) 3865.
[29] S. Dunkle, R.J. Helmich, K.S. Suslick, J. Phys. Chem. C 113 (2009)
11980.
[30] W. Kohn, L.J. Sham, Phys. Rev. 140 (1965) A1133.
[31] J.P. Perdew, A. Ruzsinszky, G.I. Csonka, O.A. Vydrov, G.E. Scuseria, L.A.
Constantin, X. Zhou, K. Burke, Phys. Rev. Lett. 100 (2008) 136406.
[32] J. Heyd, G.E. Scuseria, M. Ernzerhof, J. Chem. Phys. 118 (2003) 8207.
[33] J. Paier, M. Marsman, K. Hummer, J. Chem. Phys. 125 (2006) 249901.
[34] J. Heyd, G.E. Scuseria, M. Ernzerhof, J. Chem. Phys. 124 (2006) 219906.
[35] G. Kresse, J. Hafner, Phys. Rev. B 47 (1993) 558.
[36] G. Kresse, J. Furthermu } ller, Phys. Rev. B 54 (1996) 11169.
[37] A.D. Becke, J. Chem. Phys. 99 (1993) 1372.
[38] A.D. Becke, J. Chem. Phys. 99 (1993) 5648.
[39] L. Schimka, J. Harl, G.J. Kresse, Chem. Phys. 134 (2011) 024116.
39
[40] K.A. McDonnell, N.J. English, M. Rahman, D. Dowling, Phys. Rev. B 86 (2012)
115306.
[41] H.J. Monkhorst, J.D. Pack, Phys. Rev. B 13 (1976) 5188.
[42] M. Gajdoš, K. Hummer, G. Kresse, J. Furthmüller, F. Bechstedt, Phys. Rev. B 73
(2006) 045112.
[43] R.H. French, H. Mullejans, D.J. Jones, J. Am. Ceram. Soc. 81 (1998) 2549.
[44] R.H. French, J. Am. Ceram. Soc. 83 (2000) 2117.
[45] H.E. Swanson, M.C. Morris, E.H. Evans, L. Ulmer, NBS Monograph (United
States), Monograph 25 (1964) 64.
[46] J.P. Perdew, in: R.M. Dreizler, J. da Providencia (Eds.), Plenum, New York, 1985.
[47] S. Park, B. Lee, S.H. Jeon, S. Han, Curr. Appl. Phys. 11 (2011) S337.
[48] J.F. Li, A.S. Bhalla, L.E. Gross, Opt. Commun. 92 (1992) 115.
[49] O. Pulci, G. Onida, R.D. Sole, Phys. Rev. Lett. 81 (1998) 5374.
[50] L. Zhang, D. Chen, X. Jiao, J. Phys. Chem. B 110 (2006) 2668.
[51] G. Xi, J. Ye, Chem. Commun. 46 (2010) 1893.