First-principles studies of electronic, optical, and vibrational properties of

polymorph
,
Liming Sun, Xian Zhao, Yanlu Li, Pan Li, Honggang Sun, Xiufeng Cheng, and Weiliu Fan

Citation: Journal of Applied Physics 108, 093519 (2010); doi: 10.1063/1.3499308

View online: http://dx.doi.org/10.1063/1.3499308
View Table of Contents: http://aip.scitation.org/toc/jap/108/9
Published by the American Institute of Physics
 JOURNAL OF APPLIED PHYSICS 108, 093519 共2010兲

First-principles studies of electronic, optical, and vibrational properties

of LaVO4 polymorph
Liming Sun,1 Xian Zhao,2 Yanlu Li,2 Pan Li,2 Honggang Sun,2 Xiufeng Cheng,2 and
Weiliu Fan1,a兲
1
Department of Chemistry and Chemical Engineering, Shandong University, Jinan 250100, China
2
State Key Laboratory of Crystal Materials, Shandong University, Jinan 250100, China
共Received 10 July 2010; accepted 2 September 2010; published online 10 November 2010兲
First-principles calculations of electronic, optical, and vibrational properties of LaVO4 polymorph
were performed with the density functional theory plane-wave pseudopotential method. The results
of the electronic structure reveal that the different coordinated structure for monoclinic LaVO4 leads
to an indirect band gap, while tetragonal LaVO4 has a direct band gap. Besides, the analysis of the
electronic structure shows ionic nature in La–O bonds and covalent nature in V–O bonds. From
further study in chemical bonding behavior, we find that the V–O covalent bonds have four types:
␴ bonding, ␲ bonding, ␲ⴱ antibonding, and ␴ⴱ antibonding states. Various optical properties,
including the dielectric function, reflectivity, absorption coefficient, refractive index, and the
energy-loss spectrum as functions of the photon energy were calculated. Our calculations indicate
that monoclinic LaVO4 has excellent dielectric properties along 关0 0 1兴 direction. In the
optical-frequency 共␻ → ⬁兲 contributed from electrons the optical properties of tetragonal LaVO4
show the isotropy, while the diagonal components of static dielectric tensors ␧共0兲 of tetragonal
LaVO4 have the ␧xx = ␧yy ⫽ ␧zz relation by adding the lattice vibration contribution 共␻ → 0兲 to the
electronic dielectric tensor. The vibrational spectra of LaVO4 polymorph have also been calculated
from first principles by the linear response method. The calculated frequencies are in good
agreement with the experimental data available for these crystals obtained by the methods of
infrared and Raman spectroscopies. The vibrational spectra of monoclinic and tetragonal LaVO4
crystal exhibit three groups of frequencies: the low-frequency 共⬍240 cm−1兲, middle-frequency
共270– 450 cm−1兲, and high-frequency region 共850– 970 cm−1兲, according to the vibration
dominated by translation of La atoms, the bending vibration of O–V–O bonds, and stretching
vibration of O–V–O bonds, respectively. Our studies report on microstructure of LaVO4 polymorph,
and provide useful information for the potential application of this material. © 2010 American
Institute of Physics. 关doi:10.1063/1.3499308兴

I. INTRODUCTION a facile hydrothermal route for preparation of the zircon-type

Lanthanide orthovanadates are important rare earth com-
pounds which have been widely applied as polarizers,1,2 laser
host materials,3,4 phosphors,5,6 and catalysts7 due to their
unique electronic structure and the numerous transition
modes involving the 4f shell of rare earth ions. Lanthanide
orthovanadates crystallize in two polymorphs, that is, mono-
clinic 共m-兲 monazite type and tetragonal 共t-兲 zircon type.
Generally, with increasing ionic radius, Ln3+ ions show a
strong tendency toward monazite-structured orthovanadate
because of its higher oxygen coordination number of 9 as
compared with 8 of the zircon one. For this reason, LaVO4
chooses the monazite type as the thermodynamically stable
state, while the other orthovanadates normally exist in the
zircon type.8,9
Among Lanthanide orthovanadates, LaVO4 is neither a
suitable host for luminescent activators10,11 nor a promising
catalyst7 owing to its ordinary monoclinic monazite structure
compared to other orthovanadates. On the contrary, tetrago-
nal zircon LaVO4 is expected to possess superior properties
and is expected to be a promising phosphor candidate, as
revealed by Yan’s research.12,13 Our group has demonstrated
a兲
Electronic mail: fwl@sdu.edu.cn.
LaVO4 nanorods/nanowires by controlling the solution
pH,14–16 without any templates and/or catalysts. Besides, we
have also synthesized lanthanide ions 共Eu3+, Sm3+, and Dy3+兲
doped monazite- and zircon-type phased LaVO4 nanocrystals
by the facile hydrothermal method, and measured the photo-
luminescence spectra. The results indicated that due to the
structural transformation, zircon-type t-LaVO4: Ln 共Ln= Eu,
Sm, and Dy兲, quite different from monazite-type one, may be
a promising red phosphor candidate.17 On that basis, great
progress recently has been made in the hydrothermal synthe-
sis of t-LaVO4 nanostructures18–20 and the investigations in
the improved luminescent behavior18,19 and catalytic
activity.20
Though LaVO4 has been widely studied in recent years
due to its important properties, to our best knowledge, no
systemic studies have been reported on its microstructure,
including electronic structure, optical properties, and vibra-
tional properties. The optical properties, such as the absorp-
tion spectrum and the dielectric function, can be used to
determine the optical band gap and electronic dielectric con-
stants, which are fundamental in the modeling of the conduc-
tion band offsets, leakage current and dielectric breakdown.
In addition, the knowledge of vibrational properties plays a

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093519-2 Sun et al. J. Appl. Phys. 108, 093519 共2010兲

TABLE I. Lattice parameters of LaVO4 polymorph.

Monoclinic Tetragonal

a b c a c
共Å兲 共Å兲 共Å兲 共Å兲 共Å兲

Present 7.0431 7.2468 6.6977 7.4267 6.5136

Experimenta ¯ ¯ ¯ 7.4578共7兲 6.5417共9兲
Experimentb 7.0434共1兲 7.2801共1兲 6.7224共1兲 ¯ ¯
Experimentc 7.043 7.279 6.721 7.437 6.553
a
Reference 9.
b
Reference 27.
c
Reference 28.

key role in understanding the structural, phase transition, and
infrared 共IR兲/Raman vibration. Thus, systemic studies on mi-
crostructure of LaVO4 polymorph are still of great impor-
tance and in demand.
In this paper, we present first-principles calculations of
the structure, electronic properties, optical properties, and vi-
brational properties of LaVO4 polymorph. The atomic posi-
tions and the unit-cell parameters were allowed to relax to
the minimum energy configuration to investigate different
crystal structure. Structural and electronic properties were
discussed to provide a sufficient explanation to the difference
of the optical and vibrational properties for LaVO4 poly-
morph. Besides, via vibrational calculations, we aim at pro-
viding a compelling assignment of the experimental Raman
and IR peaks to specific phonons which would allow one to
identify the vibrational signature of the different structural
units in the crystals.
The remainder of this paper is organized as follows. A
brief description of our computational method is given in
Sec. II. The results and discussion are examined in Sec. III,
followed by a summary of our conclusions in Sec. IV.
was 0.03 eV/Å, the maximum displacement was 0.001 Å,
and the stress was 0.05 GPa, respectively. For all equilibrium
structures, the Mulliken populations were investigated using
a projection of the plane-wave states onto a linear combina-
tion of atomic orbitals set,25,26 which is widely used to per-
form charge transfers and population analysis. The electronic
band structure, density of states 共DOS兲 spectra, optical prop-
erties, and vibrational properties were performed under the
optimized structure.
III. RESULTS AND DISCUSSION
A. Structural and electronic properties
After the total energy minimization and full lattice and
atomic relaxation were conducted, the equilibrium lattice pa-
rameters have been computed and the results are given in
Table I with the experimental values. The calculated values
of the lattice constants of the two LaVO4 phases are very
close to the experimental results. Figure 1 shows the opti-
mized structures. The monoclinic monazite-type phase
LaVO4 关Fig. 1共a兲兴 is the thermodynamically stable state. In

II. COMPUTATIONAL DETAILS

The calculations reported in this paper were performed
with the plan-wave pseudopotential density functional theory
共DFT兲 method as implemented in the CASTEP code,21 using
norm-conserving pseudopotentials22 and a plane-wave ex-
pansion of the wave functions. The exchange-correlation po-
tential was described by generalized gradient approximation
共Ref. 23兲 with the Perdew–Burke–Ernzerhof 共Ref. 24兲
scheme. The unit cell containing four LaVO4 formula units
was used for m-LaVO4 structure. While, to reduce the com-
putational cost, we chose the primitive cell which contains
two LaVO4 formula units for t-LaVO4 structure. Under the
restriction of the symmetry, the total energy was minimized
via varying the cell parameters and the atomic positions to
obtain the structure optimization. Lattice constants and inter-
nal positions in unit cells were fully optimized. The conver-
gence criteria for structure optimization and energy calcula-
tion were set to fine quality with a kinetic energy cutoff of
680 eV and the k-point meshes of 4 ⫻ 3 ⫻ 4 for m-LaVO4,
and 3 ⫻ 3 ⫻ 4 for t-LaVO4. Geometry optimization was done
before single point energy calculation and the self-consistent
FIG. 1. 共Color online兲 Crystal structure of LaVO4 and oxygen coordination
convergence accuracy was set at 1.0⫻ 10−5 eV/ atom. The around the La atom in LaVO4 polymorph. 共a兲 共a⬘兲 m-LaVO4, stable at am-
convergence criterion for the maximal force between atoms bient pressure, and 共b兲 共b⬘兲 t-LaVO4.
093519-3 Sun et al.
FIG. 2. Electronic band structures of LaVO4 polymorph along high symme-
try directions in the BZ.
m-LaVO4 with space group of P21 / n, the lanthanide atom
prefers nine oxygen coordination numbers, as shown in Fig-
ure 1a⬘, and the vanadium atom is centered in a distorted
tetrahedron with four different V–O distances, 1.720 Å,
1.728 Å, 1.729 Å, and 1.739 Å, respectively. The tetragonal
zircon-type LaVO4 crystallizes in the I41 / amd space group,
in which the lanthanide atom is eightfold coordinated by
oxygen atoms 关Fig. 1共b⬘兲兴 and the VO43− group exhibits
regular V-center tetrahedron with uniform bond-lengths
共V–O: 1.731 Å兲.
Electronic band structure of LaVO4 polymorph along the
high symmetry directions are illustrated in Fig. 2. The Fermi
level is chosen to be the zero of the energy scale. As shown
in Fig. 2共a兲, a remarkable feature in the band structure of
m-LaVO4 is that the maximum of the valence band and the
minimum of conduction band are not at the same point in the
Brillion zone 共BZ兲. Between the valence band and the con-
duction band there is an indirect gap D-E of 3.42 eV, and a
direct gap at D of 3.54 eV, which is close to 3.5⫾ 0.2 eV
from the experimental result measured from optical absorp-
tion edge.29 From Fig. 2共b兲, we find that t-LaVO4 has a direct
band gap of 3.01 eV at the highly symmetric G point, which
is different from the band structure owning an indirect band
gap of m-LaVO4. However, we are not aware of any experi-
mental data or theoretical calculations for the band structure
of t-LaVO4, so we consider the present results may provide a
helpful reference for experimental work.
The bands can be assigned according to the total and
partial densities of states 共PDOS兲 of m- and t-LaVO4, as
J. Appl. Phys. 108, 093519 共2010兲
FIG. 3. 共Color online兲 Total and partial DOS of LaVO4 polymorph. 共a兲
m-LaVO4, and 共b兲 t-LaVO4.
depicted in Figs. 3共a兲 and 3共b兲. The two phases show some
similar features in the DOS curves. We can see that the en-
ergy bands between ⫺17.0 and ⫺15.0 eV mainly consist of
O 2s electronic states with some admixture of the La 6p
states. The PDOS in the region of ⫺13.7 and ⫺11.5 eV is
mostly composed of La 6p states with some mixture of
O 2s states. More importantly, we note a hybridization be-
tween O 2p and V 3d states in energy from the Fermi level,
indicating the covalent bonding character in the compounds.
In order to verify this result, we have calculated the elec-
tronic density distribution of m- and t-LaVO4 as shown in
Fig. 4. We chose to construct contour plots in the plane con-
taining O–V–O bonds and their nearest-neighboring La at-
oms. The charge-density plots in Fig. 4 show a dense mixture
of charge density between the V and O atoms, indicating a
distinct degree of covalent bonding between V and O atoms.
The bonding states of V–O bonds lied in the top of the va-
lence bands 共−4.0– 0 eV兲, and the corresponding antibond-
093519-4 Sun et al.
FIG. 4. 共Color online兲 Electron density contour maps from 0 to 4.6927 e / Å3
for LaVO4 polymorph. 共a兲 m-LaVO4, and 共b兲 t-LaVO4.
ing states are located in the bottom of the conduction bands
共3.0–5.5 eV兲. Because of the different energies of O 2p and
V 3d orbital, the PDOS for O 2p and V 3d states shows
their asymmetric distribution in the bonding and antibonding
bands. The bonding bands has a larger O 2p contribution,
but the antibonding band has a larger V 3d contribution.
Furthermore, the shape of the DOS for the top of the valence
bands 共−4.0– 0 eV兲 has two main features both for m- and
t-LaVO4. The lower portion of the bands has contributions
from O 2p and V 3d states, while the upper portion con-
tains states of primarily O 2p character.
To investigate the chemical bonding behavior of V–O
bonds in-depth, we have constructed the electron density
contour plots of the occupied and unoccupied states for m-
and t-LaVO4, as shown in Figs. 5 and 6. We have used the
plane containing O–V–O bonds to construct a series of con-
tour diagrams for various partitions of the electronic charge
densities of m- and t-LaVO4. Since the plots for m- and
t-LaVO4 look so similar to each other, we present the plots
for m-LaVO4 as an example. From Fig. 5 and the DOS
analysis, it is evident that the lower portion of the valence
bands 共−4.0– −2.1 eV兲 for m-LaVO4 are dominated by ␴
bonding states formed from the O 2p and the V 3d states
关Fig. 5共a兲兴, while the upper portion of the valence bands
共−2.1– 0 eV兲 are dominated by ␲ bonding states formed
from the O 2p with somewhat less density associated with
the V 3d states 关Fig. 5共b兲兴. Figures 5共c兲 and 5共d兲 show the
dominance of ␲ⴱ bonding states in the lower bottom portion
共3.1–3.9 eV兲 and ␴ⴱ bonding states in the upper portion 共3.9–
4.6 eV兲 of the conduction bands, both of which are formed
FIG. 5. 共Color online兲 Contour plots of the electronic charge density asso-
ciated with the valence and conduction bands of m-LaVO4. 共a兲 The lower
portion of the valence bands 共−4.0⬃ −2.1 eV兲, 共b兲 the upper portion of the
valence bands 共−2.1⬃ 0 eV兲, 共c兲 the bottom portion of the conduction
bands 共3.1⬃3.9 eV兲, and 共d兲 the upper portion of conduction bands
共3.9⬃4.6 eV兲.
J. Appl. Phys. 108, 093519 共2010兲
FIG. 6. 共Color online兲 Contour plots of the electronic charge density asso-
ciated with the valence and conduction bands of t-LaVO4. 共a兲 the lower
portion of the valence bands 共−4.0⬃ −1.5 eV兲, 共b兲 the upper portion of the
valence bands 共−1.5⬃ 0 eV兲, 共c兲 the bottom portion of the conduction
bands 共3.0⬃4.2 eV兲, and 共d兲 the upper portion of the conduction bands
共4.2⬃5.3 eV兲.
from the O 2p and V 3d states. The plots for t-LaVO4 show
very similar distributions to those of m-LaVO4, as shown in
Fig. 6.
Due to the different symmetry between m- and t-LaVO4,
the shape of the DOS curves for m-LaVO4 has some differ-
ences with t-LaVO4. In the region of −4.0– 0 eV, m-LaVO4
has two main peaks, while there are three main peaks for
DOS curves of t-LaVO4. Moreover, t-LaVO4 phase has ad-
ditional conduction-band contributions from the La 4f states
at approximately 5–5.5 eV above the bottom of the conduc-
tion band, which can be related to the different local envi-
ronment of La atoms in the two crystals. In the universal
electronic structure for the transition metal/rare earth oxide,30
the top of the valence bands are derived from O 2p states,
while the transition metal d states dominate the bottom of the
conduction bands. And these d states split into doublets in
the conduction bands and separate the optical band gap with
the ionic gap, which we will discuss later.
As for the complicated chemical bonding behavior in
LaVO4 crystals, we performed the corresponding Mulliken
charge and bond population of m- and t-LaVO4 in Table II to
analyze the bonding character quantitatively. It is well
known that the absolute magnitudes of the atomic charges
yield by the population analysis have little physical meaning,
since they are highly sensitive to the atomic basis set. But we
still can find some useful information by considering the
relative values of Mulliken population. For m-LaVO4, the
Mulliken charges are determined to be 1.54e for La atoms,
1.11e for V atoms, and −0.66e for O atoms, indicating that
the electrons transfer from La atoms and V atoms to O atoms
are 1.54e and 1.11e, respectively. The value of the Mulliken
charges for t-LaVO4 given in Table II is similar to the mono-
clinic phase. Besides, we note an interesting phenomenon by
calculating the average Mulliken overlap population between
the La–O and V–O bonds. In the case of m-LaVO4, with
increasing the coordination of the La atoms up to 9 and
lower symmetry, there are nine different La–O bonds 共bond
population: 0.22, 0.21, 0.21, 0.18, 0.16, 0.15, 0.11, 0.10, and
0.02; bond length: 2.465, 2.472, 2.480, 2.484, 2.505, 2.536,
2.629, 2.671, and 2.897 Å兲, while t-LaVO4 has two different
La–O bonds 共bond population: 0.21 and 0.09; bond length:
093519-5 Sun et al. J. Appl. Phys. 108, 093519 共2010兲

TABLE II. Mulliken charge 共兩e兩兲 and bond population of LaVO4 polymorph.

Length
Phases Species s p d f Total Charge Bonds Population 共Å兲

m-LaVO4 La 2.18 6.02 1.04 0.21 9.46 1.54 共La– O兲1–9 0.22–0.02 2.897–2.465
V 0.18 0.39 3.32 ¯ 3.89 1.11 共V – O兲1 0.75 1.720
O 1.86 4.80 ¯ ¯ 6.66 0.66 共V – O兲2 0.72 1.728
共V – O兲3 0.72 1.739
共V – O兲4 0.71 1.729
t-LaVO4 La 2.20 5.94 1.08 0.22 9.44 1.56 共La– O兲1 0.21 2.441
V 0.19 0.36 3.31 ¯ 3.86 1.14 共La– O兲2 0.09 2.523
O 1.87 4.81 ¯ ¯ 6.68 ⫺0.68 V–O 0.73 1.731

2.441 and 2.523 Å兲. Moreover, due to the V atoms centered

in a distorted tetrahedron, the monoclinic phase has four dif-
ferent V–O bonds 共bond population: 0.75, 0.72, 0.72, and
R共␻兲 = 冏 冑冑
␧1共␻兲 + j␧2共␻兲 − 1
␧1共␻兲 + j␧2共␻兲 + 1
冏 2
,

␣共␻兲 = 冑2␻关冑␧21共␻兲 + ␧22共␻兲 − ␧1共␻兲兴1/2 ,

0.71兲, compared with the tetragonal phase owning only one
type of V–O bonds 共bond population: 0.73兲. From this infor-
mation, we can determine that the VO4 units exhibit covalent
binding, as we discussed above, and the La atoms can be n共␻兲 = 关冑␧21共␻兲 + ␧22共␻兲 + ␧1共␻兲兴1/2/冑2,
considered as ions. As shown in Fig. 4, since there is no
obvious electron density accumulation in the regions of k共␻兲 = 关冑␧21共␻兲 + ␧22共␻兲 − ␧1共␻兲兴1/2/冑2,
La–O, we obtain that the bonding behavior between the La
and O atoms is the ionic nature. L共␻兲 = ␧2共␻兲/关␧21共␻兲 + ␧22共␻兲兴.
The imaginary part of the dielectric function ␧共␻兲 for
LaVO4 polymorph are shown in Fig. 7. The real and imagi-
B. Optical properties nary parts of the dielectric function is associated with the
interband transitions, where the intraband transitions are ig-
The optical properties of LaVO4 polymorph are deter-
nored because only in metallic materials the intraband tran-
mined by the dielectric function ␧共␻兲 = ␧1共␻兲 + i␧2共␻兲, which
sitions are considered.34 For m-LaVO4, the peak of ␧2共␻兲 at
is mainly contributed from the electronic structures. The di-
5.9 eV mainly arises from the electron transition between
electric function is a very important parameter for a material
O 2p and V 3d orbitals, and the peak at 20.6 eV corre-
because it is the fundamental feature of the linear response to
sponded mainly to the transition from O 2s to V 3d orbitals.
an electromagnetic wave and determines uniquely the propa-
For t-LaVO4, peaks at 6.3 eV and 20.2 eV are also ascribed
gation behavior of the radiation within. The imaginary part
to the transition from O 2p to V 3d and from O 2s to V 3d
␧2共␻兲 of the dielectric function ␧共␻兲 could be calculated
states, respectively. In addition, at low-frequency range,
from the momentum matrix elements between the occupied
there are two steep rises in ␧2共␻兲 for both m-LaVO4 and
and unoccupied wave function and is given by

2e2␲
␧2 = 兺 兩具␺c兩ûr兩␺kv典兩2␦共Eck − Ekv − E兲,
⍀␧0 k,v,c k

where ⍀ is the unite cell volume, û is the vector defining the

polarization of the incident electric field, ␻ is the light fre-
quency, e is the electronic charge, and ␺ck and ␺kv are the
conduction and valence band wave functions at k, respec-
tively. Due to the dielectric function describing the causal
response, the real part ␧1共␻兲 of the dielectric function can be
evaluated from ␧2共␻兲 using the Kramer–Kroning relations,31

␧ 1共 ␻ 兲 = 1 + 冉 冊冕
2
␲ 0
⬁
d␻⬘
␻ ⬘2␧ 2共 ␻ ⬘兲
␻ ⬘2 − ␻ 2
.

Other optical properties, such as reflectivity R共␻兲, absorption

coefficient ␣共␻兲, the real part of the refractive index n共␻兲,
the imaginary part of the refractive index k共␻兲, and energy-
loss spectrum L共␻兲, can also be obtained from ␧1共␻兲 and FIG. 7. 共Color online兲 The real part and the imaginary part of the dielectric
␧2共␻兲 共Refs. 32 and 33兲 function ␧共␻兲 for LaVO4 polymorph: m-LaVO4 and t-LaVO4.
093519-6 Sun et al. J. Appl. Phys. 108, 093519 共2010兲

electrons for t-LaVO4, which indicates that it may have good

optical properties, and has far-reaching research significa-
tion.
While reporting on the properties of LaVO4 we will
touch on a theoretical issue in the determination of the di-
electric constants. In high dielectric constant materials, the
large static constant is mostly of vibrational origin. The value
␧共0兲 = ␧␻→⬁ + ␧␻=0 is dominated by the lattice vibrational
component ␧␻=0 共typically upward of 10–15兲 over the elec-
tronic contribution ␧␻→⬁ 共typically of 3–5兲. The lattice part
depends quadratically on the ratio of effective dynamical
charges 共polarization change upon atomic motion兲 to the fre-
quency of IR active modes35,36
4␲e2 z z
␧␻␣␤=0 = 兺 ␭␣ ␭␤ ,
⍀ ␭ ␻␭2

with
FIG. 8. 共Color online兲 The real part ␧1共␻兲 and imaginary part ␧2共␻兲 of the
Zi,ⴱ ␣␤␰i,␭␤
z ␭␤ = 兺
dielectric function ␧共␻兲 of m-LaVO4 phase corresponding to different direc-
,
tions: ␧xx, ␧yy, and ␧zz, and inset shows off-diagonal element ␧xz.
i␤
冑M i

t-LaVO4. In the imaginary part ␧2共␻兲 for m-LaVO4, one oc-
curs at 3.5 eV and the other at 4.6 eV, while for t-LaVO4, the
two steep rises lies at 3.0 eV and 4.5 eV, respectively. The
former value is the optical band gap, while the latter one is
the ionic gap. The values of optical band gap are consistent
with our former calculation. Due to the anisotropy of the
monoclinic crystal, the dielectric function ␧共␻兲 of m-LaVO4
has four nontrivial components: ␧xx, ␧yy, ␧zz, and ␧xz, as
shown in Fig. 8. The off-diagonal component ␧xz is much
smaller than the diagonal components. And the anisotropy in
the optical properties occurs mainly in the energy regions
0–10 and 17–23 eV, especially along 关0 0 1兴 direction, and in
the other energy region, the anisotropy is not displayed ob-
viously. In the energy range of 0 and 10 eV, there are three
peaks at 4.0 eV, 5.5 eV, and 8.1 eV for ␧zz 2 , whereas other
components have two peaks. Moreover, the component of ␧zz 2 bigger than other components. Table III shows the optical-
has a peak located at 19.6 eV, the located energy of which is
lower than other directions. While the function ␧共␻兲 of
t-LaVO4 has all off-diagonal components equal to zero, but
symmetry assures that ␧xx = ␧yy ⫽ ␧zz. The interesting phe-
nomenon occurring in our calculation is the presence of the
isotropy in the optical-frequency 共␻ → ⬁兲 contributed from
the mode charge vector, ⍀ the system volume, J Zⴱi the effec-
tive charge tensor, and M i the mass of atom i, ␰ជ , and ␻ the
eigenvector and eigenfrequency of mode ␭, and a, ␤ Carte-
sian indexes.
From the real part ␧1共␻兲 of the dielectric function for m-
and t-LaVO4 in Fig. 7, we can obtain the electronic contri-
bution of the static dielectric constants for the monoclinic
and tetragonal phase, which is 5.3 and 5.0 in our calculation.
Combining with the lattice vibration contribution of 18.1 and
14.1 calculated from linear responses method within the den-
sity functional perturbation theory 共DFPT兲, the total static
dielectric constants are 23.4 and 19.1 for m-LaVO4 and
t-LaVO4, respectively. Because m-LaVO4 mainly shows an-
isotropy along 关0 0 1兴 direction in optical properties, it can
be seen from Fig. 8, the component of ␧zz 1 共0兲 is 5.83 which is
frequency 共␻ → ⬁兲 and low-frequency 共␻ = 0兲 dielectric ten-
sors of m- and t-LaVO4 corresponding to different directions.
The static dielectric tensors ␧共0兲 are calculated by adding the
lattice vibration contribution to the electronic dielectric ten-
sor. The component of ␧zz共0兲 for m-LaVO4 is 27.67 which is
much bigger than other components 关␧xx共0兲 = 21.92, ␧yy共0兲

TABLE III. The optical-frequency 共␻ → ⬁兲 and low-frequency 共␻ → 0兲 dielectric tensors of LaVO4 polymorph.

Monoclinic

␻→⬁ ␻→0
x y z x y z

5.13 0 0.014 16.79 0 0.49

0 5.04 0 0 17.02 0
0.014 0 5.83 0.49 0 21.884

Tetragonal

4.95 0 0 12.67 0 0
0 4.95 0 0 12.67 0
0 0 4.95 0 0 16.88
093519-7 Sun et al.
FIG. 9. 共Color online兲 Reflectivity R共␻兲, absorption coefficient a共␻兲, real
part of the refractive index n共␻兲, imaginary part of the refractive index k共␻兲,
and electron energy-loss functions L共␻兲 for LaVO4: m-LaVO4 and t-LaVO4.
= 22.06兴. It is indicated that m-LaVO4 has excellent dielec-
tric properties along 关0 0 1兴 direction. Though t-LaVO4
shows isotropy in the optical-frequency 共␻ → ⬁兲, the diago-
nal components of static dielectric tensor ␧共0兲 of t-LaVO4
have the ␧xx = ␧yy ⫽ ␧zz relation by adding the lattice vibration
contribution 共␻ → 0兲 to the electronic dielectric tensor, i.e.,
the component of ␧xx共0兲 is 17.62, which is equal to ␧yy共0兲,
while the component of ␧zz共0兲 is 21.83. It is important to
note that the calculations are carried out for a perfect static
crystal at 0 K and no zero-point vibration is considered,
while the experimental data are obtained at room tempera-
ture under which the effect of vibration are not ignorable.
To have more insight into the optical properties in
LaVO4 polymorph, the calculated results of reflectivity R共␻兲,
absorption coefficient a共␻兲, real part of the refractive index
n共␻兲, imaginary part of the refractive index k共␻兲, and the
energy-loss spectrum L共␻兲 are shown in Fig. 9. The reflec-
tivity spectrum of m-LaVO4 indicates a reflective range from
0 to 40.0 eV, in contrast, t-LaVO4 has a broader reflective
range covering from 0 to 45.0 eV. Moreover, there are two
main peaks for m-LaVO4 at 11.2 and 26.4 eV, which could
be interpreted as the interband transitions, i.e., the electron
transitions from the valence to conduction bands. The R共␻兲
of the tetragonal phase has a series of small peaks from 0 to
30 eV. The absorption coefficient indicates the fraction of
energy lost by the electromagnetic wave when it passes
through a unit thickness of the material. At low-energy re-
gion, the steepest increase in the absorption coefficient de-
fines the optical band gap. The values of 3.5 and 3.0 eV are
extracted from our calculation for m- and t-LaVO4, respec-
tively, which are in agreement with the previous discussion
derived from the threshold rise in ␧2共␻兲. What’s more, the
absorption coefficient a共␻兲 of m-LaVO4 is narrower than
t-LaVO4, the former is about 3–38 eV while the latter is
about 3–43 eV. This phenomenon indicates that we may ob-
serve transparent LaVO4 crystal under experimental condi-
J. Appl. Phys. 108, 093519 共2010兲
tion. In the dispersion curve of the refractive index,
m-LaVO4 exhibits similar feature with t-LaVO4. From the
real part of the refraction, the low-frequency static refractive
index for m- and t-LaVO4 is equal to 2.3 and 2.2, respec-
tively.
Besides, the electron energy-loss function L共␻兲 is also
an important factor describing the energy loss of a fast elec-
tron traversing in a material, and the characteristic associated
with the plasma resonance could be represented by the peaks
of L共␻兲 spectra. The plasmon peak shows the collective ex-
citation of the loosely bound valence electrons into the un-
occupied energy levels in the conduction bands. The posi-
tions of peaks in L共␻兲 spectra, corresponding to the plasma
frequency, indicate the transition from the metallic property
关␧1共␻兲 ⬍ 0兴 to the dielectric property 关␧1共␻兲 ⬎ 0兴 for a mate-
rial. In addition, the peaks of L共␻兲 point out the trailing
edges in the reflection spectra, for instance, the peak of L共␻兲
for m-LaVO4 is at 27.1 eV, and correspond to the abrupt
reduction in R共␻兲. With regard to t-LaVO4, broad peaks cor-
respond to the slow descent of reflectivity. For m-LaVO4,
there is an additional peak at 12.9 eV in the L共␻兲 spectra due
to a net transition of La 6p electron to V 3d states. Unfor-
tunately, the related spectroscopic data are insufficient at
present.
C. Vibrational properties
Vibrational properties were obtained by the use of the
linear response method, within DFPT. In order to evaluate
the accuracy of our calculations for vibrational properties,
we consider the results obtained for m-LaVO4 first. The
group symmetry decomposition into irreducible representa-
tions of the P21 / n point group at the G point yield a sum of
2Bu + Au for three acoustic modes and 16Bu + 17Au + 18Ag
+ 18Bg for the 69 optical modes, which contain 36 Raman-
active modes 共18Ag + 18Bg兲 and 33 IR-active modes 共16Bu
+ 17Au兲, as listed in Table IV in comparison with previous
Raman and IR experimental data.7,37 The calculated frequen-
cies at G point are assigned to the measured peaks obtained
by the methods of IR and Raman spectroscopies, indicating
our calculations are in good agreement with the experimental
peaks available. We present the calculated IR absorption
spectra for m-LaVO4 as well as the theoretical positions of
the Raman peaks in Fig. 10共a兲. Due to the low symmetry of
m-LaVO4, many peaks appear in the IR absorption spectra,
and several peaks are so close to each other that they become
one broad peak. We find that the vibrational frequencies can
be divided into three regions: the low-frequency region
共⬍240 cm−1兲, the middle-frequency region 共270– 450
cm−1兲, and the high-frequency region 共850– 970 cm−1兲. Be-
cause of the great mass of La atoms, the low-frequency re-
gion mainly comes from the translation of La atoms. The
middle-frequency region involves the bending vibration of
O–V–O bonds, and the high-frequency region originates
from the stretching vibration of O–V–O bonds. Furthermore,
there are there strong peaks at 866, 882, and 920 cm−1, and
one relatively weak peak at 910 cm−1 in the high-frequency
093519-8 Sun et al. J. Appl. Phys. 108, 093519 共2010兲

TABLE IV. Vibrational frequencies of LaVO4 polymorph.

m-LaVO4 t-LaVO4

Raman IR Raman IR Silent

Mode Frequency Mode Frequency Mode Frequency Mode Frequency Mode Frequency

Ag 65 Au 74 Eg 110 Eu 144 B1u 89

Bg 66 Bu 82 B1g 115 A2u 193 A2g 148
Ag 84 Au 91 Eg 138 Eu 223 A1u 316
Bg 91 Au 111 Eg 193 Eu 289 B2u 417
Ag 97 Bu 118 B1g 211 A2u 402 B2u 913
Bg 108 Au 139 B2g 252 Eu 859
Bg 120 Bu 142 A1g 337 A2u 892
Ag 126 Bu 153 Eg 352
Ag 136 Au 154 B1g 425
Ag 142 Bu 157 Eg 889
Bg 143 Au 177 B1g 894
Bg 170 Bu 196 A1g 923
Ag 173 Au 211
Bg 178 Au 230
Ag 203 Bu 235
Bg 210 Au 274
Bg 218 Bu 281
Ag 232 共206a兲 Au 288
Bg 292 Bu 326
Ag 310 Au 341
Bg 315 Au 358
Ag 324 Bu 372
Ag 334 Bu 396
Ag 367 共334a兲 Bu 404
Bg 378 Au 446
Bg 394 Au 866 共835b兲
Ag 405 Bu 877
Bg 406 共400a兲 Bu 882 共850b兲
Ag 865 共839a兲 Au 884
Bg 877 Bu 910 共881b兲
Ag 883 Au 916
Bg 911 Bu 920
Ag 916 Au 950
Ag 925
Bg 934 共912a兲
Bg 965
a
Experimental frequency from Ref. 37.
b
Experimental frequency from Ref. 7.

region of IR absorption spectra, which agrees with peaks at
835, 850, and 881 cm−1 in IR experimental spectroscopy. In
order to show a clear picture of the vibration patterns, we
plot the atomic displacements of m-LaVO4 corresponding to
the Raman and IR experimental peaks in S1 and S2 in Ref.
38. In IR experimental spectroscopy, the measured peak at
835 cm−1 can be identified to be the Au mode, and the peaks
at 850 and 881 cm−1 correspond to the Bu mode. All of these
peaks come from the stretching vibration of O–V–O bonds.
From Raman experimental spectroscopy, the peak at
206 cm−1 for Ag mode consists the torsion for VO4 units
with La atoms almost still, and the peaks at 334 and
400 cm−1 are Ag and Bg modes, respectively, with the bend-
ing vibration of O–V–O bonds, and the measured peaks at
839 and 912 cm−1, according to Ag and Bg modes, respec-
tively, originates from the stretching for O–V–O bonds.
We now analyze the vibrational frequencies of t-LaVO4.
For t-LaVO4, the lattice vibration spectrum consists of 36
vibration modes, and the 33 zone-center optical phonon
modes decompose according to
⌫opt = 5Eg + 4Eu + 4B1g + 3A2u + 2A1g + 2B2u + A1u + A2g
+ B1u + B2g ,
where the A2u and Eu modes are IR active and the A1g, B1g,
B2g, and Eg modes are Raman active with A1u, A2g, B1u, and
B2u modes silent. The G point calculated vibrational frequen-
cies of t-LaVO4 are listed in Table IV. As shown in the IR
spectra in Fig. 10共b兲, it can be found that there are two strong
peaks at 859 and 892 cm−1, three relatively weak peaks at
144, 193, and 223 cm−1, and two very weak peaks at 289
and 402 cm−1. To obtain a clear picture of the vibration pat-
093519-9 Sun et al.
FIG. 10. 共Color online兲 IR absorption spectra for LaVO4 polymorph and the
Raman frequencies 共vertical lines兲 are also indicated. 共a兲 m-LaVO4 and 共b兲
t-LaVO4.
terns, we chose the primitive cells to describe the atomic
displacements of t-LaVO4 corresponding to the calculated IR
peaks in S3 in Ref. 38. We find t-LaVO4 has similar vibra-
tional patterns in the three regions with m-LaVO4, i.e., the
low-frequency, middle-frequency, and high-frequency re-
gion, according to the vibration dominated by translation of
La atoms, the bending vibration of O–V–O bonds, and the
stretching vibration of O–V–O bonds, respectively. But there
are still some differences in the low-frequency region be-
tween the two phases. From IR spectra, the lowest Eu mode
at 144 cm−1 consists the translational movement of La atoms
and VO4 units along the y-axis, and another Eu mode at
222.57 cm−1 mainly come from the rotation of VO4 units
along x-axis. The A2u mode, located at 193 cm−1, originate
from the translational motions of La atoms and VO4 units
along the z-axis. For Raman peaks, the Eg modes at 110, 138,
and 193 cm−1 all involve the translational motions of La
atoms and VO4 units along the y-axis, and the B1g modes at
115 and 211 cm−1 represent the translation of La atoms and
VO4 units along the z-axis. Moreover, it can be seen from
Fig. 10共b兲, vibrational peaks for t-LaVO4 are fewer than the
m-LaVO4. That may because the decreased number of vibra-
tion peaks for the t-LaVO4 is in accordance with the lower
coordination number 共8兲 and high symmetry 共D2d兲 of the
La3+ ions, both of which contribute to the relatively simple
vibration spectra compared with that of the m-LaVO4. To
date, we have not found any experimental data or theoretical
calculations for the IR and Raman spectra of t-LaVO4, so our
results may have a role of forecast.
IV. CONCLUSIONS
In the present study, first-principles calculations are used
to investigate the structure, electronic properties, optical
properties, and vibrational properties of m- and the t-LaVO4.
The band-structure plots were obtained, indicating m- and
t-LaVO4 has an indirect and direct band gap, respectively.
From electron-density contour plots, Mulliken charge and
J. Appl. Phys. 108, 093519 共2010兲
bond population of the systems, we obtain that La–O and
V–O bonds exhibit ionic and covalent nature, respectively.
From our in-depth study, we find that the shapes of valence-
band and conduction-band DOS have two main features, and
the V–O bonds have four corresponding types: ␴ bonding, ␲
bonding, ␲ⴱ antibonding, and ␴ⴱ antibonding states. In the
PDOS of LaVO4 polymorph, t-LaVO4 has additional
conduction-band contributions from La 4f states at approxi-
mately 5–5.5 eV above the bottom of the conduction band,
due to the different local environment of La atom in the two
crystals. We further present studies of the optical properties
of m- and t-LaVO4. The dielectric function was obtained
within linear response theory, with full matrix elements. For
m-LaVO4, the anisotropy in the optical properties occurs in
the energy regions 0–10 and 17–23 eV, and our calculation
indicated that m-LaVO4 has excellent dielectric properties
along 关0 0 1兴 direction. t-LaVO4 shows the isotropy in the
optical-frequency 共␻ → ⬁兲, which may indicates that it has
far-reaching research signification. But the diagonal compo-
nents of static dielectric tensors ␧共0兲 of t-LaVO4 show the
␧xx = ␧yy ⫽ ␧zz relation, when we considered adding the lattice
vibration contribution 共␻ → 0兲 to the electronic dielectric ten-
sor. From the dielectric function, the other optical properties,
such as absorption spectrum, reflectivity, refractive index,
and energy-loss spectrum can be obtained. The calculated
Raman and IR data provide powerful and effective tool for
resolving the structure from analogous crystalline com-
pounds. We divide the phonon vibrational frequency into
three regions: the low-frequency region 共⬍240 cm−1兲 origi-
nates from the movements dominated by translation of La
atoms; the middle-frequency region 共270– 450 cm−1兲 is aris-
ing from the bending vibration of O–V–O bonds; the high-
frequency region 共850– 970 cm−1兲 is dominated by the vi-
brational displacements of stretching vibration of O–V–O
bonds. Besides, we find that vibrational peaks for tetragonal
LaVO4 are fewer than monoclinic LaVO4 due to the lower
coordination number 共8兲 and high symmetry 共D2d兲 of La3+
ions. Our studies may lead to significance research meaning
and application value.
ACKNOWLEDGMENTS
This work is supported by the National Natural Science
Foundation of China 共Grant Nos. 50802056 and 50721002兲,
973 Program of China under Grant No. 2009CB930103,
Youth Scientist 共Doctoral兲 Foundation of Shandong Province
of China under Grant No. BS 2009CL038, and the Indepen-
dent Innovation Foundation of Shandong University
共IIFSDU兲 under Grant No. 2009TS016.
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