Solid State Communications 333 (2021) 114290

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Solid State Communications

journal homepage: http://www.elsevier.com/locate/ssc

Ab initio study of the phonon and thermodynamic properties of the scheelite

MWO4 (M = Ba, Sr or Ca) compounds
I.P. Carvalho, A.F. Lima, M.V. Lalic *
Physics Department, Federal University of Sergipe, 49100-000, São Cristóvão, SE, Brazil

A R T I C L E I N F O A B S T R A C T

Communicated by: F. Peeters In this work, we performed the calculations based on density functional theory with different exchange and
correlation energy approximations and employed the method of the constant force within the harmonic
Keywords: approximation, to study the phonon and thermodynamic properties of the three MWO4 (M = Ca, Sr or Ba)
Scheelite compounds compounds with scheelite-type structure. In the first part of the work, we carried out an analysis of the per­
phonons
formance of the local density approximation (LDA) and generalized gradient approximation of the Perdew-
Thermodynamic functions
Burke-Ernzerhof revised for solids (GGA-PBEsol) on the computed phonon density of states, specific heat at
DFT calculations
constant volume, entropy and Gibbs free energy of the scheelite BaWO4 compound. Comparisons between
calculated and experimental data showed that the GGA-PBEsol approach exhibited better performance. In the
second part of the work, we extended the study of the thermodynamic properties to the SrWO4 and CaWO4
compounds, which are not presented in the literature, using the GGA-PBEsol approximation. It was found that
the magnitude of the specific heat at the constant volume at high temperature respects the following order:
BaWO4 > CaWO4 > SrWO4. Moreover, it was verified a relation between M2+ ionic radius in the scheelite MWO4
(M = Ba, Sr or Ca) and their entropy, Gibbs energy, and Helmholtz free energy.

1. Introduction
Metal tungstates (MWO4) are represented by a large number of
compounds that at ambient condition crystallize at either scheelite
tetragonal structure (space group I41/a for M = Ba, Sr, Ca, Eu or Pb) or
wolframite monoclinic structure (space group P2/c for M = Co, Cd, Fe,
Mg, Ni or Zn) [1,2]. The scheelite tetragonal compounds are important
technological materials because of their luminescent [3–6],
up-conversion [7,8], and photocatalytic properties [9,10]. They are also
used as laser-host crystals [11,12]. Under high hydrostatic pressure, the
scheelite tetragonal structure can undergo many structural phase tran­
sitions, a phenomenon that is intensively discussed in the literature
[13–18].
Both experimental and theoretical studies have been carried out on
the structural and phonon properties of the scheelite MWO4 (M = Ba, Sr
or Ca) compounds in order to elucidate the structural phase transitions
under high hydrostatic pressure [13,15–18]. Most of the theoretical
studies were based on density functional theory (DFT) calculations [19,
20]. The results, in general, agree very well with the experimental ones.
On the other hand, the thermodynamic properties of these compounds
have not been so much explored. The most detailed study has been
realized recently for the scheelite BaWO4 compound [21]. In this study,
the heat capacity at constant pressure was measured in the range of
5.7–304 K. Based on this property, the authors calculated the entropy,
enthalpy, and Gibbs free energy as a function of the temperature. The
heat capacity of the scheelite BaWO4 compound was also measured and
calculated by Suda et al. [22].
To achieve more detailed insight into the thermodynamic properties
of the scheelite MWO4 (M = Ba, Sr or Ca) compounds, in this work we
performed a detailed and comparative investigation of some of the
thermodynamic proprieties of these materials using DFT calculations.
Employing this calculation methodology, the phonon frequencies need
to be computed first, using a specific exchange and correlation (XC)
energy functional, and then the thermodynamic functions can be
calculated on the base of these phonon frequencies [23,24]. We
analyzed the effects of two different XC functionals (local density
approximation (LDA) [25] and generalized gradient approximation
GGA-PBEsol [26]) on the computed phonon and thermodynamic prop­
erties of the scheelite BaWO4 compound, which is, in terms of experi­
mental results, the best documented. This kind of analysis is important

* Corresponding author.
E-mail address: mlalic@academico.ufs.br (M.V. Lalic).

https://doi.org/10.1016/j.ssc.2021.114290
Received 23 January 2021; Received in revised form 22 March 2021; Accepted 25 March 2021
Available online 30 March 2021
0038-1098/© 2021 Elsevier Ltd. All rights reserved.
I.P. Carvalho et al. Solid State Communications 333 (2021) 114290

to guide future ab initio calculations of phonon and thermodynamic Table 2

properties of the MWO4 compounds at their different crystalline phases Calculated (with PBEsol and LDA functionals) and experimental lattice param­
since there is no consensus of which XC functional exhibits the best eters and volumes (V) of the scheelite MWO4 (M = Ba, Sr or Ca) compounds. The
performance [27–29]. experimental result are taken from Ref. [10].
The present paper has two principal objectives: (1) to analyze and a(Å) c(Å) V (Å3)
compare the performances of the LDA and GGA-PBEsol XC functionals BaWO4
on the phonon and thermodynamic properties of the scheelite BaWO4 Expt. 5.615 12.722 401.04
compound, and (2) to extend the study of the thermodynamic properties PBEsol 5.617 12.645 398.90
to others two scheelites (SrWO4 and CaWO4), which is absent in the LDA 5.626 12.389 392.10
SrWO4
literature. Thus, the first part of the paper will focus on the comparison Expt. 5.421 11.952 351.27
between calculated (using both LDA and GGA-PBEsol) and experimental PBEsol 5.415 11.877 348.20
phonon total density of states, specific heat at constant volume, entropy, LDA 5.447 11.573 343.30
and Gibbs free energy of the BaWO4 compound. In the second part, they CaWO4
Expt. 5.250 11.393 314.03
will be analyzed the thermodynamic properties of the SrWO4 and
PBEsol 5.240 11.318 310.70
CaWO4 compounds, based on the usage of the XC functional (LDA or LDA 5.184 11.351 305.04
GGA-PBEsol) with better performance.

2. Method and computational details inside) have been constructed. In total, 10 distorted 1 × 1 x 2 supercells
were generated to obtain the Hellmann-Feynman forces, from which the
The calculations were performed using the Elk [30] and PHONOPY force constant matrices (in the limit of harmonic approximation) were
codes [23]. Elk is an all-electron full-potential (FP) linearized derived. Based on the latter, the eigenvalue problem of the dynamical
augmented-plane wave (LAPW) plus local orbital code based on the matrix is resolved, and the phonon frequencies are calculated. The
DFT. In the LAPW electronic structure calculation method, the crystal­ procedure applied in this work is known in the literature as the direct-
line space is divided into two distinct regions: the muffin-tin (MT) force constant method [35,36]. Because of our limited computational
spheres, centered on the atomic nuclei, and the space between them (the capability, a larger supercell was not tested. However, the results that
interstitial region) [31,32]. In the first, the electronic wave function is will be presented in section 3.1 agree well with the experimental ones.
expanded in terms of the partial waves, while in the second in terms of Based on this fact, we concluded that the size of the supercell simulated
the plane waves. Table 1 shows the radii of the MT spheres (RMT) and in this work is satisfactory. To build the distorted supercells, find the
the valence electronic states chosen for the present calculations. They number of them and compute the phonon dispersion, it was employed
are similar to those utilized in previous calculations of the structural, the PHONOPY code which read the crystalline structure information and
electronic, and optical properties of the scheelite MWO4 (M = Ba, Sr or output-forces from Elk. Once the phonon frequencies ωkj (k: wave vec­
Ca) compounds [33]. The valence electronic states were treated using a tor; j: band index) are known, using the thermodynamic relations a
scalar relativistic scheme, while the core ones are treated fully relativ­ number of thermal properties of the solids can be computed as functions
istically [34]. Within the atomic spheres, the partial waves were of temperature [23]: specific heat at constant volume (CV), entropy (S),
expanded up to lmax = 10, while the number of the plane waves in the Helmholtz free energy (F), enthalpy (H) and Gibbs free energy (G).
interstitial was limited by the cut-off at Kmax = 7.0/RMT, where RMT ( / )
∑ (ℏωkj )2 exp ℏωkj kB T
refers to the O atom sphere. The charge density was Fourier expanded up CV = kB [ ( / ) ]2
to Gmax = 16, and a 3 × 3 x 2 k-point grid was used for the Brillouin k,j
kB T exp ℏωkj kB T − 1
zone integration.
1 ∑ ∑ [ ]
For the total-energy calculations, electronic exchange and correla­ S= ℏωkj cot
ℏωkj
− kB ln 2 sinh
ℏωkj
tion (XC) effects have been simulated by LDA [25] and GGA-PBEsol [26] 2T k,j 2kB T k,j
2kB T
functionals. All the internal atomic positions have been relaxed using
both of these functionals. The stopping criterion for moving the atoms 1∑ ∑ [ ( / )]
F= ℏωkj + kB T ln 1 − exp − ℏωkj kB T
was that the maximum residual forces sensed by the atoms were less 2 k,j k,j
than 10− 6 Ha/bohr. After this procedure, the lattice parameters have
been relaxed, again by applying both of the functionals. The results are ∫T
presented in Table 2. H(T) = CV (T)dT (using: ​ CV ≈ CP ​ for ​ solids ​ [21] )
Table 2 demonstrates that both the LDA and the PBEsol functionals 0
reproduce well the experimental lattice parameters, but the PBEsol is
more successful. The differences between the PBEsol calculated and G = H − TS
experimental volumes are: − 0.54% (for BaWO4), − 0.85% (for SrWO4)
and − 1.05% (for (CaWO4), while these differences between the LDA 3. Results and discussion
calculated and experimental volumes are higher: − 2.22% (for BaWO4),
− 2.24% (for SrWO4) and − 2.86% (for CaWO4). 3.1. Thermodynamic properties of the BaWO4: performance of the LDA
To extract force constants, the 1 × 1 x 2 supercells (with 24 atoms and GGA-PBEsol XC functionals

The top of Fig. 1 shows the calculated phonon total density of states
Table 1 (PTDOS) of the scheelite BaWO4 compound, using both the LDA and
Muffin-tin radii (RMT, in atomic units) and valence states adopted in the present GGA XC functionals, and compare the results with the experimental
calculations. spectrum determined from inelastic neutron scattering [13].
Element RMT (a. u.) Valence states The experimental spectrum from 0 to 60 meV can be divided into
20
Ca 1.90 3s23p64s2 three main structures (peaks) centered at ~10 meV, ~20 meV and ~43
38
Sr 2.00 4s24p65s2 meV. As can be seen, both LDA and GGA calculations reproduce these
structures.
56
Ba 2.10 5s24d105p66s2
74
W 1.70 5s24d105p66s24f145d4 The LDA theoretical curve correctly centers the positions of the first
8
O 1.40 2s22p2

2
I.P. Carvalho et al. Solid State Communications 333 (2021) 114290

properties of the BaWO4.

Fig. 2 shows three computed thermodynamic properties (specific
heat at constant volume, CV, entropy, S, and Gibbs energy, G) of the
scheelite BaWO4 compound, compared with the experimental data [21,
37]. Cv (T) and S(T) are calculated from formulas (9) and (11) presented
in Ref. [23], while G from formulas (27) and (28) presented in Ref. [21],
using the fact that, in general, the Cv and Cp in solids are very similar
[23,27,38]. All of these formulas are listed at the end of section 2. The
temperature range considered in Fig. 2 is limited to the temperature
range of available experimental results. In the next subsection, it will be
presented the computed thermodynamic functions of the BaWO4 in the
extended temperature range, up to 1000 K, as well as for the SrWO4 and
CaWO4 materials.
Comparing the Cv computed with LDA and GGA XC functionals, it is
seen that the LDA agrees a little bit better with the experimental data
[37]. However, in another study, which took into account the
Dulong-Petit and Kopp’s law, it was estimated that the Cv of the BaWO4
crystal should be 117 JK− 1mol− 1 at 300 K [38]. This result could be
more realistic than that of Ref. [37] because, in general, the Cv and Cp in
solids are very close to each other [23,27,38]. According to Ref. [21],
the Cp of the BaWO4 system at high temperatures should be approxi­
mately 120 JK− 1mol− 1, which agrees with the result of Ref. [38]. Thus,
based on all these available results, we estimate that the GGA XC
functional better describes the Cv of the aforementioned material.
Considering now the S and G thermodynamic functions, it is seen that at
lower temperatures both LDA and GGA results agree with the

Fig. 1. Top: phonon total density of states (PTDOS) of the scheelite BaWO4,
calculated using the LDA and the GGA XC functionals and compared to the
PTDOS data from inelastic neutron scattering experiment [13]. Bottom: partial
phonon density of states (PPDOS) calculated using the GGA functional.

two lowest energy peaks, but invert their intensities. It fails to describe a
valley between the second and the third structure, dislocates the energy
position of the latter, and fails to reproduce its intensity. On the other
hand, the GGA curve reproduces fairly well the positions of the first two
lowest energy peaks but describes pretty well their intensities. It de­
scribes satisfactorily the valley between the second and the third
experimental peaks and dislocates the position of the third structure, but
account for its intensity correctly. On the base of this analysis, we
evaluated that the GGA curve exhibits a little better agreement with the
experimental data than the LDA one.
The bottom graph in Fig. 1 shows the phonon partial density of states
(PPDOS) computed with the GGA XC functional. By comparing the
PTDOS and PPDOS, it can be seen that the first, lowest energy peak of
the spectrum is formed mainly of the Ba atom vibration modes, while the
second and third peaks are formed by O atom modes. The W atom vi­
bration modes contribute to the formation of the first peak only. This
description is consistent with the atomic masses in BaWO4 compound, i.
e., m(W) > m (Ba) > m(O). A quite similar characterization of the
PTDOS of the BaWO4 is achieved on the base of the LDA calculations as
well (not shown here). It should be noted that both GGA and LDA ap­
proaches produce spurious peaks in PTDOS (originated from O vibra­
tions) in the range of energies between 50 and 60 meV. This
Fig. 2. Calculated thermodynamic properties (specific heat at constant volume,
disagreement with the experiment is probably a consequence of the
CV, entropy, S, and Gibbs energy, G) of the scheelite BaWO4 compound. These
relatively small supercells constructed to extract the force constants in results are compared with the experimental data [21,37]. The Cv experimental
our calculations. As will be shown later, it does not affect a good curve was extracted from Ref. [37], while the S and G experimental curves were
agreement between the calculated and experimental thermodynamic extracted from the supplementary material of Ref. [21].

3
I.P. Carvalho et al. Solid State Communications 333 (2021) 114290

experimental ones [21]. However, for higher temperatures, the LDA

deviates considerably from the experimental data, while the GGA
approximate to them.
On the base of the comparisons exhibited in Figs. 1 and 2, we
conclude that the GGA has a little bit better performance than the LDA
for the calculation of the phonon and thermodynamic properties of the
scheelite BaWO4 compound. Therefore, we found a more appropriate to
perform the calculation of the thermodynamic properties of the other
two scheelite (SrWO4 and CaWO4), for which there is no published
experimental and theoretical data, with the GGA-PBEsol XC functional,
instead of the LDA one.

3.2. Thermodynamic properties of the scheelite MWO4 (M = Ba, Sr or

Ca) compounds

Based on the conclusions stated in the previous subsection, we per­

formed the calculations of the thermodynamic properties of the SrWO4
and CaWO4 compounds using the DFT + GGA-PBEsol computed phonon
frequency spectra, shown in Fig. 3. The obtained results are compared
with those of the BaWO4 (also calculated in the present work), which
allows us to infer about the thermodynamic properties of three scheelite
MWO4 (M = Ba, Sr or Ca) compounds.
Fig. 4 shows the specific heat at constant volume, CV, entropy, S,
Gibbs energy, G, and Helmholtz free energy, F, up to the temperature of
1000 K. The melting temperatures for these materials are well above the
latter, i.e., 1775 K for BaWO4 [38], 1808 K for SrWO4 [39] and 1873 K
for CaWO4 [40]. Experimental results for SrWO4 and CaWO4 were not
found in the literature, but the good agreement between the theory and
the experiment in the case of the BaWO4 system gives us confidence that
the presented new results are reliable.
Fig. 4 demonstrates that the S, G, and F of the SrWO4 and CaWO4
compounds are very similar. Their curves are practically superposed
(blue and red) in the whole temperature range. These results may be a
consequence of similar ionic radii of the Sr2+ (1.26 Å) and Ca2+ (1.12 Å)
Fig. 4. Specific heat at constant volume, CV, entropy, S, Gibbs energy, G, and
ions in their respective compounds [10]. In the scheelite tetragonal
Helmholtz free energy, F, as functions of the temperature, calculated for three
body-centered crystal, these ions occupy the M position in the MO8
MWO4 (M = Ba, Sr or Ca) compounds on the base of the DFT + GGA-PBEsol
dodecahedron local structure. phonon frequency spectra.
On the other hand, the BaWO4 compound presents higher S and -G,
and lower F values in relation to the SrWO4 and CaWO4 compounds
the Cv of the MWO4 (M = Ba, Sr, Ca) compounds can be noticed. Bellow
since the ionic radius of the Ba2+ ion (1.42 Å) is significantly larger than
the 200 K, the Cv of the SrWO4 and CaWO4 compounds are very close to
those of the Sr2+ and Ca2+ ions [10].
each other and lower than the Cv of the BaWO4 system. Above 200 K, the
The CV computed for three materials shows behavior that is typical
CV of the CaWO4 increases in relation to the SrWO4. Above room tem­
for the other solid materials as well, i. e, exhibits a T3 dependence in the
peratures, the order of magnitude of Cv of the scheelites is BaWO4 >
low-temperature regime and becomes constant for higher temperatures
CaWO4 > SrWO4.
(Dulong-Petit limit) [27–29]. However, significant differences between

Fig. 3. Phonon frequency spectra of the SrWO4 and CaWO4 compounds, shown along the P→Γ→X path within the Brillouin zone.

4
I.P. Carvalho et al.
4. Conclusions
In this work, we performed an ab-initio study of the phonon and
thermodynamic properties of the three tetragonal scheelite MWO4 (M =
Ba, Sr, Ca) compounds. For that purpose, it was employed the direct-
force constant method within the harmonic approximation. We used
the Elk code [30] for relaxation of the interatomic forces and PHONOPY
software [23] to compute the force constants, phonon frequencies, and
thermodynamic properties. In the first part of the manuscript, we
analyzed the performance of the LDA [25] and GGA-PBEsol [26] XC
functionals in predicting the phonon density of states, specific heat at
constant volume, entropy, and Gibbs energy of the scheelite BaWO4
system. The results showed that the GGA-PBEsol XC functional exhibited
better agreement with experimental results [13,21,38]. Based on this
fact, it was calculated the specific heat at constant volume, entropy,
Gibbs energy, and Helmholtz free energy for all three scheelites up to the
temperature of 1000 K, using the phonon frequencies provided by the
DFT + GGA-PBEsol calculations. The thermodynamic functions for the
SrWO4 and the CaWO4 were presented for the first time. It was found
that the magnitude of the specific heat at constant volume for the three
systems at high temperatures respect the following order: BaWO4 >
CaWO4 > SrWO4. Moreover, it was verified a relation between M2+ ionic
radius in the MWO4 (M = Ba, Sr or Ca) compounds and their entropy,
Gibbs energy, and Helmholtz free energy.
Credit authors
I.P. Carvalho: calculations, analysis of the results. A. F. Lima:
analysis of the results, original draft preparation, writing. M. V. Lalic:
analysis of the results, writing, reviewing.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgments
The authors acknowledge the CNPq, CAPES, and FAPITEC (Brazilian
funding agencies) for financial support and CENAPAD-SP for computa­
tion facilities.
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