Journal of Alloys and Compounds 547 (2013) 81–85

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Journal of Alloys and Compounds

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

First-principles study of structural, vibrational and dielectric properties of double

perovskites Ba2LnSbO6 (Ln = Sm, Gd, Dy and Y)
Karandeep, H.C. Gupta ⇑, S. Kumar
Department of Physics, Indian Institute of Technology, Hauz Khas, New Delhi 110 016, India

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

Article history: The structural, vibrational and dielectric properties of Ba2LnSbO6 (Ln = Sm, Gd, Dy and Y) type double per-
Received 30 July 2012 ovskites in the space group Fm 3  m have been investigated for the first time using the pseudopotential
Received in revised form 23 August 2012 plane wave method based on density functional theory (DFT) under local density approximation (LDA)
Accepted 23 August 2012
and linear response formalism. The lattice constants, along with the Raman and the infrared wavenum-
Available online 31 August 2012
bers at zone center are calculated and assigned. The calculated values of the lattice constants, Raman and
the infrared wavenumbers are in very good agreement with respective experimental values. The bulk
Keywords:
modulus, pressure derivative, Born effective charges and dielectric constants have also been calculated
Rare earth alloys and compounds
Crystal structure
and discussed.
Phonons Ó 2012 Elsevier B.V. All rights reserved.
Dielectric response
Computer simulations

1. Introduction powerful tools for theoretical studies of these properties. Hence

Double perovskites of type A2BB0 O6 have been studied for many
years because of their scientific and technological importance. In
1995 Kurian et al. [1] have found that double perovskites of type
Ba2LnSbO6 (Ln = Sm, Gd, Dy and Y) can be used as substrate for
the high temperature superconducting materials. Since then a
number of research groups have studied different properties of
these compounds [2–11]. X-ray diffraction studies have estab-
lished that Ba2LnSbO6 (Ln = Sm, Gd, Dy and Y) belongs to cubic
Fm 3  m space group [2–5]. Recently, Konopka et al. [6] have stud-
ied the variation of dielectric constant of Ba2YSbO6 with tempera-
ture. Further Vijayakumar et al. [7,8] have measured dielectric
constants of nanocrystalline Ba2GdSbO6 and Ba2DySbO6 oxides.
Properties of these materials are affected quite strongly by the dis-
tribution of Ln and Sb cations over the octahedral sites. Raman and
infrared spectroscopy is an attractive technique to investigate
these effects. Thus, Vijayakumar et al. [10] studied the Raman
and Infrared phonons of nanocrystalline Ba2LnSbO6 (Ln = Sm, Gd,
Dy and Y). Earlier, we had calculated the force constants in
Ba2YSbO6 and Ba2SmSbO6 compounds using Wilson GF-matrix
method [11].
To our best knowledge no theoretical studies of lattice con-
stants, phonons and dielectric constants based on first principle
formalism has been done in these materials belonging to Fm 3 m
space group. First-principles calculations offer one of the most
⇑ Corresponding author. Tel.: +91 11 26591345; fax: +91 11 26862037.
E-mail address: hcgupta@physics.iitd.ac.in (H.C. Gupta).
in this paper an attempt has been made to investigate the struc-
tural, vibrational and dielectric properties of Ba2LnSbO6 (Ln = Sm,
Gd, Dy and Y) belonging to Fm 3  m space group by pseudopotential
plane wave method within the framework of density functional
theory (DFT) under the local density approximation (LDA) and lin-
ear response formalism using quantum ESPRESSO code [12].
2. Computational details
All calculations are performed by using quantum ESPRESSO dis-
tribution, which is based on density functional theory with plane-
wave pseudopotential method [12]. Ultrasoft pseudopotentials
with local density approximation (LDA) as parameterized by Per-
dew and Zunger [13] are used in the calculations. Ultrasoft pseud-
opotentials for yttrium(Y) and oxygen (O) are taken from the
Vanderbilt group site [14], whereas ultrasoft pseudopotentials for
barium (Ba), antimony (Sb) and lanthanides (Ln = Sm, Gd, Dy) are
generated by considering 6s 6p, 5s 5p 5d and 5s 6s 5p 6p 5d, as va-
lance states respectively. These pseudopotentials include non-
linear core correction to account for large overlap between core
and valance states. Kinetic energy cutoffs for wavefunctions and
charge density are 80 Ry, 800 Ry respectively and a 4  4  4
Monkhorst–Pack k-point mesh [15] is used for Brillouin zone sam-
plings of electronic states. The structures are relaxed by taking
convergence threshold for forces and pressure to be 0.0001 eV/Å
and 0.5 kbar respectively.
Born effective charge tensors, phonon frequencies and dielectric
permittivity tensors are obtained as second-order linear-response

0925-8388/$ - see front matter Ó 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.jallcom.2012.08.106
82 Karandeep et al. / Journal of Alloys and Compounds 547 (2013) 81–85

derivatives of the total energy with respect to external electric or
atomic displacements within the framework of density functional
perturbation theory (DFPT) [16,17].
3. Results and discussion
3.1. Crystal structure
The Ideal double perovskites A2BB0 O6 have cubic structure with
Fm 3  m space group with one formula unit in primitive unit cell. In
this structure B, B0 cations occupy octahedral sites 4a(0,0,0) and
4b(0.5,0,0) respectively and A cations, oxygens occupy the
8c(0.25,0.25,0.25) and 24e(x,0,0) Wyckoff sites respectively. Struc-
ture of Ba2LnSbO6 (Ln = Sm, Gd, Dy and Y) in Fm 3  m space group is
shown in Fig. 1. The calculated and observed lattice constants, oxy-
gen 24e(x) parameter and bond distances along with calculated
bulk modulus and its first derivative are given in Table 1. It is clear
from this table that lattice parameters of Ba2YSbO6, Ba2DySbO6,
Ba2GdSbO6 and Ba2SmSbO6 differ from observed value by
0.32%, 0.24%, 0.33% and 0.19% respectively, whereas
difference in internal parameter x for oxygen atoms in Ba2YSbO6,
Ba2DySbO6 and Ba2SmSbO6 is 0.0019, 0.0027, and 0.0067 respec-
tively. Clearly the calculated values of lattice constants and oxygen
internal parameters are in excellent agreement with the observed
values. An increase in lattice constant of double perovskites with
the increase in B cation ionic radii for both the experimental and
calculated values is observed, this variation is shown in the
Fig. 2. All calculated values of lattice constants are smaller than
the observed values, which is consistent with the fact that LDA
overbinds the crystal and underestimates the lattice constant. Cal-
culated and observed bond distances are also in excellent agree-
ment with each other. The similar values of lattice constants and
bonding distances in Ba2YSbO6 and Ba2DySbO6 is due to similar io-
nic radii of Y+3 (0.900) and Dy+3 (0.912) ions. Bulk modulus and its
pressure derivative are obtained by fitting a third-order
BirchMurnaghan equation of state defined as [18]:
8" #3 " 2 #2 " 9
 2  23 #=
9V 0 B0 < V 0 3 0 V0 3 V0
EðVÞ ¼ E0 þ  1 B0 þ 1 64
16 : V V V ;
ð1Þ
where V 0 is the equilibrium volume and B0 is bulk modulus evalu-
ated at V 0 , B00 is the pressure derivative of bulk modulus also eval-
uated at V 0 .
The fitted energy versus volume curves for Ba2LnSbO6 (Ln = Sm,
Gd, Dy and Y) are shown in Fig. 3 and the calculated values of bulk
modulus and pressure derivative are given in Table 2. No experi-
mental or theoretical results are available to compare the calcu-
lated bulk modulus and its pressure derivatives. However, Lufaso
et al. [19] have found bulk modulus of Ba2YTaO6 to be
157(16) GPa in Fm 3  m structure and the present calculated values
of bulk modulus lie in this range. The values of bulk modulus of
Ba2YSbO6 and Ba2DySbO6 are almost same as these compounds
have almost same volume and the decrease in values of bulk mod-
ulus in going from Ln = Dy to Gd to Sm compounds is due to the in-
crease in volumes of respective compounds.

3.2. Vibrational modes

The primitive unit cell of Ba2LnSbO6 (Ln = Sm, Gd, Dy and Y)

contains one formula unit, thus there are thirty modes of vibration
 m structure. In this structure, Ba atoms occupy 8c sites of
in Fm 3
Td symmetry, Ln and Sb atoms occupy 4a and 4b sites of Oh sym-
metry and oxygen atoms are in 24e sites of C4m symmetry. The total
number of zone center modes for Fm 3  m space group is

Ccryst
vib ¼ CBa þ CLn þ Csb þ CO

¼ ðF1u þ F2g Þ þ F1u þ F1u þ ðA1g þ Eg þ F1g þ F2g þ F2u þ 2F1u Þ

¼ A1g þ Eg þ F1g þ 2F2g þ F2u þ 5F1u ð2Þ

Fig. 1. Conventional unit cell of Ba2LnSbO6 (Ln = Sm, Gd, Dy and Y) in Fmbar3m (O5h )
space group (Z = 4, ZB = 1). Blue, gray, green and red balls represent Ba, Ln, Sb and O
atoms respectively. (For interpretation of the references to color in this figure
legend, the reader is referred to the web version of this article.)
Further, out of these normal modes A1g, Eg and 2F2g are Raman
active and 4F1u modes are infrared active. Also, one F1u is acoustical
and F1g, F2u modes are optically inactive.
Vijayakumar et al. [10] observed four Raman active modes (A1g,
Eg and 2F2g) as strong or medium intense bands at 760, 572, 375

Table 1
Calculated and observed [2–5] structural parameters along with calculated bulk modulus, B and pressure derivative of bulk modulus, B0 of Ba2LnSbO6 (Ln = Sm, Gd, Dy and Y) in
Fmbar3m (O5h ) space group (Z = 4, ZB = 1).

Ba2YSbO6 Ba2DySbO6 Ba2GdSbO6 Ba2SmSbO6

Obs. Cal. Obs. Cal. Obs. Cal. Obs. Cal.
a(Å) 8.4240 8.3966 8.4247 8.4049 8.474 8.4461 8.50908 8.49312
O(x) 0.2636 0.2617 0.2646 0.2619 – 0.2632 0.258 0.2647
Sb–O(Å) 1.9914 2.0012 1.9832 2.0012 – 1.9998 2.0591 1.9985
Ln–O(Å) 2.2206 2.1971 2.2292 2.2012 – 2.2232 2.1953 2.2481
Ba–O(Å) 2.9805 2.9703 2.9811 2.9733 – 2.9882 3.0091 3.0054
B (in GPa)a – 161.0 – 161.8 – 159.2 – 156.1
B0 – 4.80 – 4.82 – 4.86 – 4.83
a  structure).
Lufaso et al. [19] have observed bulk modulus of Ba2YTaO6 to be 157(16) GPa (a similar compound with Fm3m
 Karandeep et al. / Journal of Alloys and Compounds 547 (2013) 81–85 83

Table 2
Calculated and observed [10] wavenumbers (in cm1) of zone center phonons in
Ba2LnSbO6 (Ln = Sm, Gd, Dy and Y) in Fmbar3m (O5h ) space group (Z = 4, ZB = 1).

Species Ba2YSbO6 Ba2DySbO6 Ba2GdSbO6 Ba2SmSbO6

Obs. Cal. Obs. Cal. Obs. Cal. Obs. Cal.
A1g 760 759.9 761 762.3 762 763.4 759 764.0
Eg 572 585.5 574 595.9 575 600.4 566 604.6
F2g(1) 380 388.8 375 388.0 375 383.7 372 378.7
F2g(2) 108 111.8 108 111.1 105 107.6 102 103.6
F1u(1) 634 627.6 629 627.6 627 630.2 623 632.7
F1u(2)a – 334.2 – 331.0 – 329.5 – 327.9
F1u(3) – 246.5 – 207.0 – 206.2 – 205.5
F1u(4) – 133.0 – 125.2 – 121.7 – 117.2
F2u – 247.2 – 246.8 – 239.9 – 231.8
F1g – 98.4 – 98.0 – 79.8 – 52.5
a
Lavat and Baran [20] observed a peak at 357, 359 cm1 for Ba2InSbO6 and
 m structure).
Ba2ScSbO6 respectively (similar compounds with Fm 3

Fig. 2. Variation of Lattice constant with B cation ionic radii of Ba2LnSbO6 (Ln = Sm,
Gd, Dy and Y) in Fmbar3m (O5h ) space group (Z = 4, ZB = 1).
and 108 cm1 respectively and one strong infrared absorption
mode around 630 cm1 along with several weak bands. The pres-
ence of weak bands can be ascribed to the impurities, local symme-
try breakdown, incomplete ordering and lowering of site
symmetry of octahedral site cations [20]. The calculated and ob-
served Raman and infrared wavenumbers given in Table 2 are in
excellent agreement with each other. It is important to mention
here that, in our earlier study of Ba2YSbO6 and Ba2SmSbO6 com-
pounds a normal coordinate analysis was performed to calculate
the inter atomic force constants by taking the Raman and infrared
frequencies as input parameters [11]. The input infrared frequen-
cies taken in the fitting process were the weak infrared modes
which appear in the Raman scattering due to lowering of site sym-
metry of octahedral site cations as given by Vijayakumar et al. [10]
rather than the single absorption mode that appears in the FT-IR
spectrum. The present calculations clearly do not justify our earlier
approach.
The displacement pattern of all atoms in Raman active modes is
shown in Fig. 4. It is clear from Eq. (2) and Fig. 4 that only oxygen
atoms move in the A1g and Eg modes while all cations are at rest.
Thus wavenumbers corresponding to these modes are determined
by the Sb–O and Ln–O bonding forces and distances. An increase in
the wavenumbers of A1g and Eg modes in going from Ln = Dy to Gd
to Sm is due to the decrease in Sb–O bonding distances. Also from
Eq. (2), we conclude that in F2g modes both barium and oxygen
atoms move, but from Fig. 4 it is clear that displacement of oxygen
atoms dominate in F2g(1) mode and displacement of barium atoms
dominate in F2g(2) mode. The wavenumbers corresponding to the
F2g(1), F2g(2) modes are influenced by the O–Sb–O and O–Ln–O
bending forces and Ba–O stretching forces respectively. The de-
crease in F2g(1), F2g(2) wavenumbers from Ba2YSbO6 to Ba2SmSbO6
is due to the increase in Ln–O and Ba–O bonding distance from Ba2-
YSbO6 to Ba2SmSbO6, respectively.
The situation is more complex in the infrared modes, since all
atoms move in the F1u modes. Vijayakumar et al. [10] observed
only one infrared mode (F1u(1)) at 630 cm1 whereas Lavat and
Baran [21] studied infrared spectra of Ba2BSbO6 (B = In, Sc) and
found two bands near at 659–615and 357–359 cm1. It is obvious
from Table 2 that the calculated F1u(1), F1u(2) modes lie in this
range. A small decrease in wavenumbers of F1u(2), F1u(3) and
F1u(4) modes as the Ln cation changes from Y to Sm indicates that
these modes can be attributed to the increase in Ln–O and Ba–O
bonding distances. A noticeable decrease in wavenumbers F1u(3)
from Ba2YSbO6 and Ba2LnSbO6 (Ln = Sm, Gd, Dy) indicates the
influence of higher masses of lanthanides than yttrium. Thus these
modes are determined mainly by the Ln–O bonds. It is also impor-
tant to mention here that the calculated trends of the changes in
going from Ln = Y to Dy to Gd to Sm for the A1g, Eg and F1u(1) modes
in case of Ba2SmSbO6 are different from that of the experimental
ones, this discrepancy in the trend is possibly due to the existence
of Ba2SmSbO6 at phase transition from rhombohedral R3  space
group to the cubic Fm 3  m space group as mentioned by Vijayaku-
mar et al. [10].

Fig. 3. Fitted energy versus volume curves along with data points for Ba2LnSbO6 (Ln = Sm, Gd, Dy and Y) in Fmbar3m (O5h ) space group (Z = 4, ZB = 1).
84 Karandeep et al. / Journal of Alloys and Compounds 547 (2013) 81–85

Fig. 4. Displacement pattern of all atoms in Raman active mode of Ba2LnSbO6 (Ln = Sm, Gd, Dy and Y) in Fmbar3m (O5h ) space group (Z = 4, ZB = 1). Here only primitive cell is
shown. Blue, gray, green and red balls represent Ba, Ln, Sb and O atoms respectively. (For interpretation of the references to color in this figure legend, the reader is referred to
the web version of this article.)

3.3. Dielectric properties tive charge tensor of oxygen (O) is anisotropic due to different
environment around oxygen. The Born effective charge of oxygen
The dispersion theory [22,23] shows that static dielectric (O), along Ln–O–Sb bond is higher in magnitude than the nominal
permittivity tensor of a crystal within harmonic approximation is ionic charge of 2, whereas Born effective charge transverse to Ln–
given by O–Sb bond is smaller than the nominal charge 2. The anomalies
$ $ $ are larger in Sm, Dy, Gd, Y and O ions than the Sb and Ba ions. Fi-
s ¼  1 þ  ionic ð3Þ nally the Born effective charges of Ba, Sb and O ions are almost
$
where  is the electronic dielectric tensor,
$
 is the ionic dielec- independent of the B-site cations (Y, Dy, Gd, Sm) with variations
1 ionic
tric tensor given by 0.32%, 0.24%, and 0.33% for Ba, Sb and O ions respectively.
The contribution of the individual modes to the static dielectric
X X Z la Zla constant l and mode effective charges Z   are given in Table 4. It is
l
ionic
ab ¼ l ¼ ð4Þ clear from Table 4 that out the four F1u modes, F1u(3) has highest
l v 0 m0 xl
2
l
mode effective charge and maximum contribution towards the sta-
where l labels the zone center (q = 0) infrared-active modes of tic dielectric constant. High frequency modes, F1u(1) and F1u(2) de-
vibrations with frequencies xl l the oscillator strength of mode spite having higher mode effective charges contribute less than the
l, Zla their effective charges in Cartesian direction a, and V the vol- low frequency mode F1u(4). The calculated electronic dielectric
ume per unit cell. Mode effective charges in Cartesian direction a tensors along with the static dielectric tensor are also shown in
for a given mode l is defined as Table 4. While the dielectric constants of Ba2YSbO6 and Ba2DySbO6
X are almost same, an increase in the dielectric constant from Dy to
ðZ l Þa ¼ Z iac ðm0 =mi Þ1=2 ðal Þic ð5Þ Gd to Sm is mainly due to the F1u(4) mode. Konopka et al. [6] have
iac
measured the dielectric constants in Ba2YSbO6 and Vijayakumar
where Z i is Born effective charge tensor for ion i, mi its mass, ðal Þic } et al. [7,8] have measured dielectric constants in nanocrystalline
the component of normalized dynamical matrix eigenvector for Ba2DySbO6 and Ba2GdSbO6. The difference between the calculated
mode l involving ion i in the c direction, and m0 an arbitrary mass, and observed dielectric constants of Ba2YSbO6, Ba2DySbO6 and
which is cancelled by the denominator of Eq. (2). We choose Ba2GdSbO6 are 4.38%, 30.42% and 47.44% respectively. Inter-
m0 = 1 amu in this work. Finally the Born effective charge tensor estingly the experimental values of dielectric constants are found
for a given ion i is defined as: to be higher than corresponding DFT calculated values and
difference between experimental and theoretical values is very
@Pa
Z iac ¼ V ð6Þ
@uic Table 3
 m (O5 )
Calculated Born effective charges of Ba2LnSbO6 (Ln = Sm, Gd, Dy and Y) in Fm 3 h
where P is the polarization of the system and uic is displacement of space group (Z = 4, ZB = 1).
ion i in direction c.
The calculated Born effective charges for Ba2LnSbO6 (Ln = Sm, Materials Z Ba Z Ln=c Z Sb Z 0

Gd, Dy and Y) are given in Table 3. The Born effective charge of bar- Ba2YSbO6 2.36923 4.09210 4.78243 [3.39170, 1.70602, 1.70602]
ium (Ba), lanthanides (Sm, Gd, Dy and Y) are larger than the nom- Ba2DySbO6 2.37191 4.10519 4.77787 [3.39844, 1.70613, 1.70613]
Ba2GdSbO6 2.37628 4.12995 4.81405 [3.42230, 1.71156, 1.71156]
inal ionic charges +2 and +3. The antimony (Sb) Born effective
Ba2SmSbO6 2.38165 4.15228 4.85110 [3.44634, 1.71690, 1.71690]
charge is smaller than the nominal ionic charge +5. The Born effec-
 Karandeep et al. / Journal of Alloys and Compounds 547 (2013) 81–85 85

Table 4
Calculated mode effective charges Z l and contribution of different infrared phonon modes to static dielectric constant for Ba2LnSbO6 (Ln = Sm, Gd, Dy and Y). Calculated values of
l and s are also given. Experimental values ofl at room temperature are given in parentheses [6–8].
Modes Ba2YSbO6 Ba2DySbO6 Ba2GdSbO6 Ba2SmSbO6

Z l u 
Z l u 
Z l u 
Z l u
F1u(1) 4.4848 1.0012 4.6822 0.9709 4.4889 0.9788 4.5632 0.9859
F1u(2) 4.2878 1.8269 4.5754 2.3170 4.5304 2.1978 4.4751 2.0632
F1u(3) 5.0739 3.7246 4.6822 4.1201 4.7087 4.1686 4.7341 4.1923
F1u(4) 3.0172 2.6900 2.8641 1.9560 3.0636 2.5302 3.2638 3.3281
1 3.6663 3.6709 3.6896 3.7100
s 12.9090(13.5) 13.0349(17) 13.5650(20) 14.2795

large in nanocrystalline Ba2DySbO6 and Ba2GdSbO6. The probable
reasons are:
(1) We have calculated the dielectric constants at absolute zero
temperature whereas the experimental values are reported
at room temperature. Although Konopka et al. [6] have stud-
ied the variation of static dielectric constant with tempera-
ture in Ba2YSbO6 oxide only. A steep increase in static
dielectric constant towards zero Kelvin indicates a new
phase in Ba2YSbO6 oxide.
(2) As we have discussed earlier that in these materials due to
the lowering of site symmetries Raman modes become infra-
red active and appear as weak bands in infrared absorption
spectra [10,19]. Higher values of the experimental static
dielectric constants may be due to the contributions of these
weak bands towards static dielectric tensors. Indeed these
modes are also found by Vijayakumar et al. [7,8] during their
study of the dielectric properties of nanocrystalline Ba2DyS-
bO6 and Ba2GdSbO6. Small difference in calculated and
experimental values of dielectric constants in Ba2YSbO6
compared to Ba2DySbO6 and Ba2GdSbO6 indicates the more
site symmetry breaking in later compounds.
4. Conclusions
The structural and vibrational properties of double perovskites
Ba2LnSbO6 (Ln = Sm, Gd, Dy and Y) have been studied for the first
time by using first-principles plane wave pseudopotential method
within the linear density approximation (LDA). The following con-
clusions are obtained:
(1) The calculated lattice parameters and the internal parameter
x for oxygen atoms in these materials are in excellent agree-
ment with the experimental values.
(2) The calculated values of bulk modulus and pressure deriva-
tive of bulk modulus for Ba2LnSbO6 (Ln = Sm, Gd, Dy and Y)
lie in the range of 156–162 GPa and 4.78–4.87 respectively.
(3) The calculated vibrational modes are in excellent agreement
with the experimental values.
(4) The Born effective charge of barium (Ba), lanthanides (Sm,
Gd, Dy and Y) are larger than the nominal ionic charges +2
and +3. The antimony (Sb) Born effective charge is smaller
than the nominal ionic charge +5 and Born effective charge
of oxygen (O) is anisotrophic. Born effective charges of Ba,
Sb and O ions are almost independent of the B-site cations
(Y, Dy, Gd, Sm).
(5) Out the four F1u modes, F1u(3) has highest mode effective
charge and maximum contribution towards the static dielec-
tric constant.
(6) Due to lowering of site symmetries Raman modes become
infrared active and appear as weak bands in infrared absorp-
tion spectra. Higher values of the experimental static dielec-
tric constants may be due to the contributions of these weak
bands towards static dielectric tensors in Ba2LnSbO6
(Ln = Sm, Gd, Dy and Y).
Acknowledgements
Two of the authors, Karandeep and S. Kumar gratefully
acknowledge the financial assistance from Council of Scientific
and Industrial Research (CSIR)-India.
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