Structural and electronic properties of BiOX (X = F, Cl, Br, I) considering Bi 5f states

Wen Lai Huang

*
, Qingshan Zhu
State Key Laboratory of Multi-Phase Complex Systems, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190, Peoples Republic of China
a r t i c l e i n f o
Article history:
Received 2 January 2009
Accepted 25 May 2009
Available online 21 June 2009
Keywords:
Density functional theory
Bismuth oxyhalide
Electronic structure
Relaxation
Photocatalyst
a b s t r a c t
Density functional theory (DFT) calculations have been performed to investigate the structural and elec-
tronic properties of BiOX (X = F, Cl, Br, I) photocatalysts, considering the Bi 5f states. Comparing with our
previous results without Bi 5f states, the present work conveys similar gap features and comparable gap
widths for the unrelaxed species, but the relaxation here causes opposite directions of atomic displace-
ments and different trends for band and gap widths. The unrelaxed BiOF exhibits a direct band gap of
3.25 eV, while the other three species present the indirect gaps of 2.62, 2.16 and 1.51, respectively.
Atomic relaxation expands the above gaps to 3.41, 2.69, 2.21 and 1.62 eV correspondingly. Analyses
based on wavefunction isosurfaces and decomposed orbitals reveal that at the valence-band tops, O
2p
z
and F 2p
z
states prevail in BiOF, O 2p
y
and X np
y
dominate in BiOCl and BiOBr, and the I 5p
x
state gov-
erns in BiOI. The conduction-band bottoms are composed mainly of the Bi 6p
z
orbital.
2009 Elsevier B.V. All rights reserved.
1. Introduction
Layered bismuth oxyhalides have demonstrated not only good
catalytic activities and selectivities in the oxidative coupling of
methane (OCM) [1], oxidative dehydrogenation of ethane (ODE)
[2,3] and n-butane [4], but also outstanding photocatalytic activi-
ties [57] and introduce a new family of promising photocatalysts.
According to the measured absorption spectra, the band gap of
BiOCl has been evaluated to be 3.46 [5] or 3.51 eV [6] within the
ultraviolet range, and the gaps of BiOBr and BiOI were determined
to be 2.91 [6] and 1.92 eV [7] respectively within the visible-light
range. Nanoparticles of BiOCl, BiOBr and BiOI have been synthe-
sized in reverse microemulsions [8], and nano-sized BiOI exhibits
a band gap up to 2.96 eV, in comparison with 1.94 eV for its bulk
material. Nanobelts and nanotubes of bismuth oxyhalides have
also been prepared via hydrothermal method, and the absorption
patterns were found to be dependent on the synthetic conditions
[9].
With respect to theoretical investigations, Zhang et al. [5] have
calculated the band structure and density of states (DOS) of BiOCl
via the TB-LMTO (tight-binding linear mufn-tin orbital) method
using local density approximation (LDA), considering 6s and 6p
states for Bi. The indirect nature obtained is in agreement with
the experimentally observed linear relationship between the
square root of the absorption coefcient and energy, though the
calculated band gap is relatively narrow. We have also reported
previously the calculation results of BiOX at the generalized
gradient approximation (GGA) level within the CASTEP code [10],
using experimental [11] or relaxed atomic positions [12], with
the Bi 5d states considered or not. The as-calculated band gap is
direct for BiOF, and indirect for the other species. Relaxation of
atomic positions elongates the Bi1X1 (or Bi2X2) distances with-
in the unit cells and shrinks the gaps. However, when we checked
the results within the Quantum-ESPRESSO package [13] with the
supplied pseudopotentials containing Bi 5f states, we obtained
similar gap features, comparable gap widths, but quite different
atomic positions after relaxation. The atoms move in the opposite
directions compared to our previous work, and the relaxation ex-
pands the band gaps. The present work will report such results,
orbitals of interest will be analysed according to their orientation
components, and the atomic charges will be evaluated using both
the Lwdin [14] and Bader [15] methods.
2. Computational details
Calculations were conducted via the plane-wave pseudopoten-
tial (PW-PP) DFT method as implemented in the Quantum-
ESPRESSO package [13]. The PerdewBurkeErnzerhof (PBE) [16]
GGA was employed for the exchange-correlation functional.
Ultrasoft pseudopotentials were used for O, F, Cl and Br, while
the TroullierMartins norm-conserving pseudopotentials were
adopted for I [17] and Bi [18]. The 2s and 2p states were consid-
ered for O with 6 electrons, and ns and np (n = 2, 3, 4 and 5 for
X = F, Cl, Br and I respectively) states were exploited for X with
7 electrons (the I 5d states were considered as well [17]). In the
norm-conserving pseudopotential of Bi, the 5d, 5f, 6s and 6p states
0927-0256/$ - see front matter 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.commatsci.2009.05.016
* Corresponding author. Address: State Key Laboratory of Multi-Phase Complex
Systems, Institute of Process Engineering, Chinese Academy of Sciences, Zhong
Guan Cun, Haidian District, P.O. Box 353, Beijing 100190, Peoples Republic of China.
Tel.: +86 10 62650558; fax: +86 10 62536108.
E-mail address: wlhuang@home.ipe.ac.cn (W.L. Huang).
Computational Materials Science 46 (2009) 10761084
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were included with total 15 electrons [18]. The pseudopotentials
of Bi, O, F and Cl were generated with the scalar-relativistic calcu-
lations, and those of Br and I were created with the non-relativis-
tic and full-relativistic calculations, respectively. The kinetic
energy cutoffs of 80 and 360 Ry were utilized respectively for
the smooth part of the electronic wave functions and the aug-
mented electron density to achieve a total-energy difference be-
low 2 meV/atom, and 18 empty orbitals were exploited,
accompanied with dense MonkhorstPack [19] k-point grids (cen-
tered at the C point) of 35 35 20 for BiOF, and 30 30 15
for BiOBr, BiOCl and BiOI to smooth the DOS curves achieved via
the tetrahedron method [20]. The Methfessel and Paxton [21]
smearing of 0.01 Ry was further applied to eliminate the unphys-
ical oscillations of the DOS plots [18]. Atomic positions were re-
laxed until all components of the residual forces were smaller
than 0.026 eV/ (0.001 Ry/bohr) using the Broyden, Fletcher, Gold-
farb, Shanno (BFGS)-based method [22], and the k-point grids of
21 21 12 for BiOF, and 18 18 9 for BiOBr, BiOCl and BiOI
were found to be ne enough to yield converged results. Band
structures were calculated along the special lines connecting the
following special points: C (0, 0, 0), X (0, 0.5, 0), Z (0, 0, 0.5), M
(0.5, 0.5, 0), R (0, 0.5, 0.5), and A (0.5, 0.5, 0.5) in the k-space.
Atomic charges were evaluated via both the Lwdin [14] (included
in the Quantum-ESPRESSO package [13]) and Bader [15] (by
means of the program developed by Henkelman et al . [23])
methods.
The structure of BiOX belongs to the tetragonal space group P4/
nmm (number 129), and the atoms occupy the following special
positions: O in 2a, X in 2c with a parameter u
X
, and Bi also in 2c
but with a different parameter u
Bi
. The unit cell of unrelaxed BiOF
is illustrated in Fig. 1 (rendered via the XCrySDen code [24]) as an
example, containing 6 atoms, and the following discussion will
implement the site notations here. For all the species, experimental
lattice constants were kept xed while the experimental atomic
positions were employed as the starting points of relaxation, and
subsequent calculations were conducted using the relaxed atomic
positions.
3. Results and discussion
3.1. Optimized atomic positions
The experimental lattice parameters [25] and relaxed atomic
positions are listed in Table 1, and some angles and distances are
provided in Table 2. As reported in our previous work [12], relaxa-
tion of atomic positions increases u
X
and reduces u
Bi
, i.e., enlarges
the Bi1X1 (or Bi2X2) distances within the unit cells, where the
incorporation of Bi 5d states offers somewhat slighter position
changes from the experimental values. For comparison, the previ-
ous results obtained with Bi 5d states have been involved in Tables
1 and 2 as well. It is obvious that the relaxation in the present work
gives a reverse trend, that is, reduces the u
X
value while increases
u
Bi
, shortening the Bi1X1 (or Bi2X2) distances within the unit
cells. The position changes incurred by the relaxation in the pres-
ent work are smaller for most cases (except for u
X
of BiOF) than
those in our previous work; namely, the present work gives smal-
ler discrepancies from the experimental positions. Such improve-
ments might originate from the additional consideration of Bi 5f
states here.
3.2. Band structures
Electronic band structures of the unrelaxed BiOX species calcu-
lated in the present work (Fig. 2, the energy zero is set at the va-
lence-band tops) are similar in appearance and distribution to
our previous results [11]. The Bi 5d states create the lowest local-
ized band, the next three low-energy occupied bands correspond
principally to the s-type orbitals (X ns, O 2s and Bi 6s for BiOF,
while O 2s, X ns and Bi 6s for the other species, sequentially),
and both valence and conduction bands are constructed by the
hybridization of Bi 6p, O 2p and X np orbitals. Generally, the orbi-
tals exhibit apparent atness in the reciprocal [001] direction (MA,
CZ and XR lines), and large dispersion in the reciprocal [100] or
[010] (CX and ZR) and [110] (CM and ZA) directions, indicating
the marked localization along the z-axis and signicant extension
along the x or y-axis. This is attributed to the different interatomic
distances along the different directions within the tetragonal cells,
where the lattice constant c presents larger values than a for all the
species. Some orbitals in the valence or conduction bands also ex-
hibit obvious dispersion along the reciprocal [001] direction, and
this corresponds to the high content of corresponding p
z
state
there. Such dispersion further shows dependence on the X atomic
number, for the inuence of the lattice constant c and the X np-
shell size.
Among the s-type bands of each species, as shown in Table 3,
the Bi 6s band exhibits the largest width due to the large radius
Fig. 1. Illustration of the unrelaxed BiOF unit cell.
Table 1
Lattice parameters (in eV) of experimental and relaxed BiOX.
Species a () c () u
X
u
Bi
BiOF 3.748 6.224 0.65 0.208
BiOF
a
0.645 0.213
BiOF
b
0.651 0.197
BiOCl 3.891 7.369 0.645 0.170
BiOCl
a
0.644 0.176
BiOCl
b
0.657 0.160
BiOBr 3.916 8.077 0.653 0.154
BiOBr
a
0.650 0.159
BiOBr
b
0.664 0.145
BiOI 3.985 9.129 0.668 0.132
BiOI
a
0.661 0.138
BiOI
b
0.677 0.125
a
Relaxed in the present work.
b
Relaxed previously [12].
W.L. Huang, Q. Zhu/ Computational Materials Science 46 (2009) 10761084 1077
of Bi 6s shell. The bandwidth corresponding to O 2s orbitals is
rather large as well, partially owing to the small interatomic dis-
tance (a=

2
p
). The narrow width of the X ns band might be ascribed
to the small radius of X ns shell. Accompanied by the increase in
the X atomic number, the bandwidth of X ns increases apparently
with the size of X ns shell, and that of O 2s declines thanks to the
increasing lattice constant a. Such inuence on the bandwidths of
Bi 6s and 5d is slight because of the large shell radii. Since the va-
lence band is the hybridization of Bi 6p, O 2p and X np orbitals, the
rst dropping and then rising of its width with the increasing X
atomic number might be attributed to the overall effect of the
increasing X np shell size, BiOBi angle, BiO and BiX distances,
and decreasing BiXBi angle. Meanwhile, considering the negligi-
ble contribution of X np to the conduction band, the increasing
BiO distance and BiOBi angle might account for the slight
reduction in W
cb
with the increasing X atomic number. Concerning
the unrelaxed species in Table 3, it can also be observed that the
bandwidths in the present work are slightly larger (but comparable
in general) than those of our previous results.
Relaxation of atomic positions in this work does not modify the
band structures apparently, but noticeable changes in bandwidths
arise. Comparing our previous relaxed results [12] with unrelaxed
ones [11] (tabulated in Tables 2 and 3), it is found that the previous
relaxation reduces the BiO distance, but increases the BiOBi
angle for each species, and increases the BiXBi angle, reduces
the Bi1X2 (or Bi2X1) distance for most species, therefore,
increasing both the W
vb
and W
cb
values. However, the present
relaxation reduces the BiOBi angle, increases the BiO distance
for each species, though reduces the Bi1X1 (or Bi2X2) distance
within the unit cell for each species, and increases the BiXBi
angle, reduces the Bi1X2 (or Bi2X1) distance for most species,
accordingly, reducing both the W
vb
and W
cb
values.
Table 2
Bond angles and interatomic distances within experimental or relaxed BiOX.
Species Angle () Distance ()
BiOBi BiXBi BiO Bi1X2 or Bi2X1 Bi1X1 or Bi2X2
BiOF 110.725 143.115 2.278 2.794 2.751 3.473
c
BiOF
a
109.348 143.206 2.296 2.793 2.688 3.536
c
BiOF
b
113.509 140.886 2.241 2.812 2.826 3.398
c
BiOCl 114.444 127.284 2.314 3.071 3.500 3.869
c
BiOCl
a
112.712 128.398 2.337 3.056 3.449 3.920
c
BiOCl
b
117.520 127.929 2.275 3.062 3.665 3.704
c
BiOBr 115.147 121.244 2.320 3.178 4.030 4.047
c
BiOBr
a
113.330 121.743 2.344 3.170 3.958 4.119
c
BiOBr
b
118.246 121.738 2.281 3.170 4.192 3.885
c
BiOI 117.670 114.118 2.329 3.358 4.893 4.236
c
BiOI
a
115.349 113.907 2.358 3.362 4.774 4.355
c
BiOI
b
120.226 114.649 2.298 3.348 5.031 4.098
c
a
Relaxed in the present work.
b
Relaxed previously [12].
c
Within two adjacent unit cells.
Fig. 2. Band structures of (a) BiOF, (b) BiOCl, (c) BiOBr and (d) BiOI calculated with experimental atomic positions.
1078 W.L. Huang, Q. Zhu/ Computational Materials Science 46 (2009) 10761084
The band-gap structures of the unrelaxed BiOX species are pre-
sented in Fig. 3, and the relaxation of atomic positions creates no
remarkable differences, as shown in Fig. 4. The unrelaxed results
are similar to our previous work [11], but the relaxed plots show
some opposite trends compared with our previous counterparts
[12]. For instance, the present atomic relaxation elevates appar-
ently one (the highest for BiOF, BiOCl or BiOBr, and the second
highest for BiOI, constructed mainly by O 2p
x
and 2p
y
states
according to the wavefunction analysis) of the six doubly degener-
ate valence-band orbitals along the MA line in energy, whereas the
previous relaxation lowers the energy of those orbitals. The transi-
tion positions (valence-band tops and conduction-band bottoms)
obtained here are similar to our previous results, and atomic relax-
ation causes no observable change. Some slight variation exists
(the valence-band top of BiOF, and the conduction-band bottoms
of BiOBr and BiOI) but is triing due to the atness of the positions.
It is acceptable to reckon that the gap in BiOF is direct or nearly
direct, and those of the other species are indirect, but the atness
of the transition position is noticeable in several cases, which
might improve the transition probability.
The wavefunction isosurfaces corresponding to the valence-
band tops and conduction-band bottoms of unrelaxed species are
presented in Fig. 5 (very similar to those of the relaxed ones). At
the valence-band top of BiOF, both O 2p
z
and F 2p
z
states prevail,
and the contribution of the former seems slightly larger. Rendering
at a higher isovalue reveals more apparently that the F 2p
z
orbital
here distributes asymmetrically (largely pointing to the Bi atomic
site along the z-axis within the unit cell) and seems to hybridize
with the F 2s orbital. For BiOCl and BiOBr, the valence-band tops
consist mainly of O 2p
y
and X np
y
orbitals, along with some contri-
bution from X ns states. The X np
y
states dominate and the part
fromO 2p
y
declines fromBiOCl to BiOBr. Within BiOI, the I 5p
x
state
dominates the valence-band top almost completely. Reducing the
isovalue shows that the O 2p
x
also confers a trivial part. As de-
scribed, in each species, the orientation of X np is parallel to that
of O 2p, which might favor their mutual overlapping. Unlike the
other three species, at the valence-band top, BiOF extends the O
2p and F 2p orbitals along the z-axis, and this holds through the
whole ZR line and a part of ZA line (near the Z point), explaining
the atter valence-band top along these lines owing to the weak
overlapping of O 2p and F 2p orbitals in the these directions per-
pendicular to the z-axis.
The conduction-band bottoms of these species are dominated
by the Bi 6p
z
orbital (which governs the lowest conduction-band
orbital (LUMO) along the whole CZ line and some parts of other
lines near the C or Z point), and due to the increasing lattice con-
Table 3
Band parameters (in eV) of experimental and relaxed BiOX.
Species W
Bi5d
W
Xns
W
O2s
W
Bi6s
W
vb
E
gap
W
cb
E
Xpeak
BiOF
a
0.38 0.41 2.94 3.00 5.00 3.25 4.58 2.05
BiOF
b
0.34 0.39 2.93 3.03 4.90 3.22 4.51 1.98
BiOF
c
0.35 0.44 2.85 2.88 4.88 3.41 4.28 2.10
BiOF
d
0.42 0.39 3.11 3.51 5.16 3.00 5.00 1.74
BiOCl
a
0.30 0.84 2.63 3.03 4.89 2.62 4.61 0.77
BiOCl
b
0.26 0.83 2.63 3.04 4.72 2.80 4.42 0.68
BiOCl
c
0.25 0.87 2.51 2.82 4.72 2.69 4.44 0.78
BiOCl
d
0.36 0.76 2.86 3.54 5.01 2.60 4.89 0.77
BiOBr
a
0.29 0.99 2.55 2.89 5.11 2.16 4.55 0.56
BiOBr
b
0.26 0.78 2.56 2.83 4.94 2.36 4.36 0.52
BiOBr
c
0.24 1.01 2.43 2.64 4.93 2.21 4.34 0.63
BiOBr
d
0.35 0.74 2.78 3.34 5.22 2.24 4.81 0.51
BiOI
a
0.28 1.38 2.40 2.97 5.50 1.51 4.46 0.65
BiOI
b
0.25 1.28 2.40 2.96 5.31 1.75 4.25 0.46
BiOI
c
0.22 1.40 2.25 2.65 5.24 1.62 4.17 0.58
BiOI
d
0.31 1.25 2.57 3.33 5.60 1.63 4.59 0.47
W
Bi5d
: bandwidth of Bi 5d orbitals; W
Xns
: bandwidth of Xns orbitals; W
O2s
: band-
width of O 2s orbitals; W
Bi6s
: bandwidth of Bi 6s orbitals; W
vb
: valence-band width;
E
gap
: band-gap width; W
cb
: conduction-band width; E
Xpeak
: the peak position of X
np DOS in the valence-band below the valence-band top.
a
Calculated in the present work using experimental lattice parameters.
b
Calculated previously using experimental lattice parameters [11].
c
Relaxed in the present work.
d
Relaxed previously [12].
Fig. 3. Band-gap structures of (a) BiOF, (b) BiOCl, (c) BiOBr and (d) BiOI with experimental atomic positions.
W.L. Huang, Q. Zhu/ Computational Materials Science 46 (2009) 10761084 1079
Fig. 4. Band-gap structures of (a) BiOF, (b) BiOCl, (c) BiOBr and (d) BiOI with relaxed atomic positions.
Fig. 5. The wavefunction isosurfaces corresponding to the valence-band tops (top) and conduction-band bottoms (bottom) of unrelaxed BiOF, BiOCl, BiOBr and BiOI (from left
to right), rendered with a same isovalue. The perspective direction and atomic sites are similar to those in Fig. 1.
1080 W.L. Huang, Q. Zhu/ Computational Materials Science 46 (2009) 10761084
stant c with the X atomic number, the Bi 6p
z
overlapping between
adjacent unit cells weakens and thus the conduction-band bottom
attens. The Bi 6p
z
distribution is severely asymmetric, and mostly
located around the O atomic layer, beneting the antibonding with
the O orbitals, and this trend is more apparent with the reducing X
atomic number. The O orbital at the conduction-band bottom is p
z
-
type for BiOF, and s-type (rendering with a high isovalue reveals
that O 2p
z
state participates as well) for the other species. The X
np
z
orbital also appears in the conduction-band bottom and shows
obvious asymmetry. With the rising X atomic number, its contribu-
tion decreases, and its main part shifts towards the adjacent Bi
atomic site along the z-axis, perhaps promoting the antibonding
hybridization with the Bi 6p
z
orbital.
The band-gap widths have also been listed in Table 3. Compara-
ble to our previous results [11], the value of unrelaxed BiOF
acquired here is slightly larger, but those of the other three are
smaller. The previous relaxation [12] narrows the gaps, but the
present relaxation widens them. Considering the available experi-
mental values (3.46 [5] or 3.51 eV [6] for BiOCl, 2.91 eV for BiOBr
[7], and 1.92 [6] or 1.94 eV [8] for BiOI), the well-known DFT
underestimation of band gap is obvious as before, though the
experiments might be conducted with different cell constants or
atomic positions.
3.3. Density of states
The unrelaxed BiOX species provide similar plots of the total
and partial density of states (PDOS) to the relaxed ones, and they
are comparable to our previous results [11,12] as well. Those of
the unrelaxed species are given in Fig. 6, within the energy range
covering all the occupied bands and the conduction band, and
the energy zero corresponds to the valence-band tops. Although
the Bi 5f and I 5d states have been incorporated in the present
calculations, they locate mainly beyond the conduction band of
each species, and their density in the displayed energy range is
negligible and has not been illustrated. The Bi 6p states contribute
the least to the valence band but dominate in the conduction band.
The X np states are triing in the conduction band, and explicate a
somewhat localized feature in the valence band, with the density
peak migrating towards the valence band top as the X atomic num-
ber increases (Table 3). As mentioned in our previous work, such a
trend might contribute somewhat to the discrepancy of the re-
ported photocatalytic activity among the BiOX species [57], anal-
ogous to the fact that the positions of d-band centers are related
with the reactivity of metal surfaces [26,27].
Although some weak bonding appears among Bi 5d, O 2s and F
2s in BiOF, or between Bi 5d and O 2s in the other species, the most
obvious hybridization outside of valence and conduction bands is
that between Bi 6s and O 2p (the I 5s states participate additionally
in BiOI). As a representative, we offer the wavefunction illustration
of such hybridization for unrelaxed BiOF in Fig. 7, along the special
lines, considering the Bi 6s-O 2p bonding (the 15th) and antibond-
ing (the 16th) orbitals. These isosurfaces are rendered with a same
isovalue to facilitate mutual comparison. Since the isosurface
appearance along the ZA line is very similar to that along the CM
line, and the case along the CX is also undistinguishable from that
along the ZR line, for simplicity, the isosurfaces on the ZA and CX
lines have not been presented here. The bonding and antibonding
orbitals along the MA and XR lines are twofold degenerate, and
on each orbital along these lines, the Bi 6s states appear only
around one Bi atomic site. Along the MA line, the Bi1 6s state over-
laps O1 2p
y
and O2 2p
x
states on the 15th orbital, and Bi2 6s state
bonds O1 p
x
and O2 p
y
states on the 16th orbital, that is, the Bi1 (or
Bi2) 6s state shows overlapping with O1 2p and O2 2p simulta-
neously. Through the XR line, however, Bi2 6s state only exhibits
bonding with O2 2p
y
on the 15th orbital, and Bi1 6s only overlaps
O1 2p
y
on the 16th orbital. Along the other three lines where no
degeneracy exists, on each orbital (the 15th or 16th), Bi 6s states
Fig. 6. The total and partial DOS of (a) BiOF, (b) BiOCl, (c) BiOBr and (d) BiOI with experimental atomic positions.
W.L. Huang, Q. Zhu/ Computational Materials Science 46 (2009) 10761084 1081
appear around both Bi1 and Bi2 atomic sites, and it is no surprise
that the overlapping appears only on the bonding orbital (the
15th), including Bi 6sO 2p
xy
(possibly the hybridization of p
x
and p
y
) on the CM line, Bi 6sO 2p
z
on the CZ line, and Bi1 6s
O1 2p
z
, Bi2 6sO2 2p
z
on the ZR line. Referring to these isosurfaces,
strong overlapping exists on both the 15th and 16th orbitals along
the MA and XR lines, and the 15th orbital on the ZR line.
In order to obtain more detailed understanding, the density
plots of p-type states have been further partitioned according to
the orbital orientation, as given in Fig. 8 for the unrelaxed species
Fig. 7. The wavefunction isosurfaces on the MA, CM, CZ, ZR and XR lines (from left to right) of the number 15 (top) and 16 (bottom) orbitals of unrelaxed BiOF, indicating the
hybridization between Bi 6s and O 2p orbitals. The perspective direction and atomic sites are similar to those in Fig. 1.
Fig. 8. The p-orbital DOS of (a) BiOF, (b) BiOCl, (c) BiOBr and (d) BiOI with experimental atomic positions.
1082 W.L. Huang, Q. Zhu/ Computational Materials Science 46 (2009) 10761084
(similar to those of the relaxed ones). The curves of p
x
states are
identical to those of p
y
ones here. From Fig. 8, it is observed that
the valence-band top is p
z
states for BiOF, but p
x
or p
y
for other spe-
cies, while the conduction-band bottom is dominated by the Bi 6p
z
orbital in each species, which is consistent with the wavefunction
rendering (Fig. 5). In the conduction band, the density curve of Bi
6p
x
or 6p
y
shows an apparent shift from that of Bi 6p
z
, towards
the high-energy range. The Bi 6p
x
or 6p
y
states also exhibit differ-
ent density distribution from the Bi 6p
z
ones in the valence band,
and enrich within the low-energy region. The density resonance
between X np
z
and X np
x
(np
y
) states is fairly well, and they govern
the localized peak in the valence band together. The density distri-
bution of O 2p
x
(or 2p
y
) does not follow that of O 2p
z
in the middle
of the valence band, but seems more dispersive.
As described in our previous work [11,12], the BiOX species
might belong to the p-to-p (O 2p and X np to Bi 6p) charge-transfer
type, and their band gaps could be evaluated by DW
cb
analo-
gous to the p-to-d charge-transfer-type transition-metal com-
pounds [28]. The charge-transfer energy D might decrease with
the reduction in either the electronegativity of the X atom or the
Madelung potential in the species. With the increasing X atomic
number, the Pauling electronegativity of X falls (3.98, 3.16, 2.96
and 2.66 for F, Cl, Br and I, respectively [29]), and the Ewald energy
of BiOX increases (341.68, 290.40, 258.45 and 203.19 Ry/
cell, respectively), showing the decreasing Madelung potential
(maybe due to the increasing BiO and BiX distances). Further
considering the insignicant (slightly decreasing) change in W
cb
in the same X order (Table 3), the monotonic reduction in band
gap seems quite reasonable. Our previous relaxation of atomic
positions [12] enlarges the W
cb
and Bi1X1 (or Bi2X2) distance
within the unit cell, and thus narrows the gap for each species,
despite the shortened BiO and Bi1X2 (or Bi2X1) distances.
The present relaxation reduces the W
cb
, strengthens the Madelung
potential (the Ewald energy decreases to 344.25, 294.52,
264.38 and 213.60 Ry/cell for BiOF to BiOI, respectively, proba-
bly due to the shortening of both Bi1X1 and Bi1X2 distances),
and thus expands the band gaps (Table 3). As to the unrelaxed
species, the present work shows smaller gaps than the previous
work [11] mainly due to the larger W
cb
values.
3.4. Atomic charges
The atomic charges calculated via the Lwdin population anal-
ysis are listed in Table 4, and some discrepancies can be found
when compared with our previous Mulliken [30] analysis results
[11,12]. However, as we know, the absolute magnitudes of both
the Mulliken and Lwdin populations have little physical meaning,
and only the relative values can be compared to achieve some use-
ful information. With the increase in X atomic number, the popu-
lations of O remain almost constant, whereas those of Bi increase
and those of X decrease (the changes occur mainly on the p-orbi-
tals), reecting the reducing oxidation capability of X. Atomic
relaxation leads to no observable difference in atomic populations.
Such trends are quite similar to our previous results [11,12]
achieved via the Mulliken approach. The Bi 5f states show small
but far from null populations, which reects the importance of
their inclusion to some extent.
The results from the Bader charge analysis program [23] are
listed in Table 4 as well. The Bader analysis method is based on
the Baders theory of atoms in molecules (AIM), where the inter-
atomic boundaries (atomic envelopes) are dened as linking all
points of zero ux in the gradient vector eld of the electron den-
sity. The physical space can thus be partitioned into non-overlap-
ping regions (atomic volumes), and each region involves
generally only one atom. Consequently, the electron density distri-
bution can be divided into atomic contributions, and integrating
the electron density within atomic volumes endows the atomic
charges. The Bader method is believed to be more reliable than
the Mulliken-type one, and has been employed extensively [31
33]. Comparing the results with those obtained via the Lwdin
population analysis reveals that the Bader method gives larger
populations for O and X, and smaller ones for Bi. However, the pop-
ulation evolution with the X atomic number exhibits a quite simi-
lar trend to that obtained with the Lwdin method.
4. Conclusion
With the incorporation of Bi 5f states, the atomic positions of
BiOX (X = F, Cl, Br and I) were optimized using the xed lattice con-
stants, and the electronic structures were calculated for both the
unrelaxed and relaxed species, within the GGA scheme. Although
the Bi 5f states are located principally above the conduction bands
in energy, showing limited occupations, they inuence the band
structures to some extent and the atomic relaxation signicantly.
The atomic displacements following the atomic relaxation in the
presence of Bi 5f states are in directions opposite to our previous
results without Bi 5f states, and the present displacements are
smaller, that is, the relaxed positions here are closer to the exper-
imental ones.
The current relaxation shortens both the Bi1X2 and Bi1X1
(within one unit cell) distances, narrows the conduction-band
widths, and broadens the gaps, while in our previous work, the
atomic relaxation of each species enlarges the Bi1X1 distance
within one unit cell, expands the conduction band, and shrinks
the gap. However, the involvement of Bi 5f states and atomic relax-
ation induces only slight changes in the transition positions for
some species. In general, the band gap of BiOF is direct, whereas
the other species exhibit indirect gaps.
Bi 6p, O 2p and X np states contribute differently to the valence
and conduction bands, and for each atom the p
x
(or p
y
) and p
z
com-
ponents exhibit different DOS as well. The conduction-band bot-
toms of all these BiOX species are composed mainly of Bi 6p
z
,
and the valence-band top is largely O 2p
z
and F 2p
z
for BiOF, O
2p
y
and X np
y
for BiOCl and BiOBr, and I 5p
x
for BiOI.
Concerning the remarkable Bi 6sO 2p hybridization, strong
bonding is found between Bi 6s and O 2p
z
on the ZR line, and
between Bi 6s and O 2p
x
(or O 2p
y
) along the MA and XR lines.
Similar to our previous Mulliken analyses, both the present
Lwdin and Bader population analyses reveal that from BiOF to
Table 4
Lwdin and Bader atomic populations (in e) within experimental and relaxed BiOX.
Species BiOF BiOCl BiOBr BiOI BiOF
a
BiOCl
a
BiOBr
a
BiOI
a
O 2s
b
1.77 1.78 1.79 1.80 1.77 1.79 1.80 1.81
2p
b
4.94 4.95 4.95 4.95 4.93 4.94 4.94 4.93
t
b
6.71 6.73 6.74 6.74 6.70 6.73 6.73 6.74
t
c
7.18 7.19 7.19 7.19 7.17 7.17 7.18 7.16
X ns
b
1.92 1.89 1.89 1.88 1.92 1.89 1.89 1.88
np
b
5.63 5.44 5.35 5.23 5.63 5.44 5.35 5.22
5d
b
/ / / 0.02 / / / 0.02
t
b
7.56 7.33 7.24 7.12 7.55 7.32 7.23 7.12
t
c
7.81 7.68 7.60 7.50 7.82 7.67 7.60 7.49
Bi 6s
b
1.79 1.84 1.85 1.85 1.79 1.84 1.85 1.85
6p
b
1.59 1.72 1.79 1.87 1.59 1.73 1.80 1.87
5d
b
9.99 9.99 9.99 10.00 9.99 9.99 10.00 10.00
5f
b
0.27 0.30 0.30 0.33 0.27 0.30 0.31 0.33
t
b
13.64 13.85 13.93 14.04 13.65 13.86 13.94 14.05
t
c
13.01 13.14 13.20 13.32 13.02 13.16 13.22 13.34
t: Total populations.
a
With relaxed atomic positions.
b
Lwdin populations.
c
Bader populations.
W.L. Huang, Q. Zhu/ Computational Materials Science 46 (2009) 10761084 1083
BiOI, the atomic populations of Bi increase while those of X
decrease, showing the reduction in oxidative capability, and that
the atomic relaxation causes no observable changes in the atomic
charges.
Acknowledgement
This work has been nancially supported by the National Natu-
ral Science Foundation of China (Grant No. 50730002).
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