Influence of the exchange-correlation functional on the quasi-harmonic lattice dynamics of II-VI semiconductors

Jonathan M. Skelton, Davide Tiana, Stephen C. Parker, Atsushi Togo, Isao Tanaka, Aron Walsh

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Abstract

We perform a systematic comparison of the finite-temperature structure and properties of four bulk semiconductors (PbS, PbTe, ZnS, and ZnTe) predicted by eight popular exchange-correlation functionals from quasi-harmonic lattice-dynamics calculations. The performance of the functionals in reproducing the temperature dependence of a number of material properties, including lattice parameters, thermal-expansion coefficients, bulk moduli, heat capacities, and phonon frequencies, is evaluated quantitatively against available experimental data. We find that the phenomenological over- and under-binding characteristics of the local-density approximation and the PW91 and Perdew-Burke-Enzerhof (PBE) generalised-gradient approximation (GGA) functionals, respectively, are exaggerated at finite temperature, whereas the PBEsol GGA shows good general performance across all four systems. The Tao-Perdew-Staroverov-Scuseria (TPSS) and revTPSS meta-GGAs provide relatively small improvements over PBE, with the latter being better suited to calculating structural and dynamical properties, but both are considerably more computationally demanding than the simpler GGAs. The dispersion-corrected PBE-D2 and PBE-D3 functionals perform well in describing the lattice dynamics of the zinc chalcogenides, whereas the lead chalcogenides appear to be challenging for these functionals. These findings show that quasi-harmonic calculations with a suitable functional can predict finite-temperature structure and properties with useful accuracy, and that this technique can serve as a means of evaluating the performance of new functionals in the future.

LanguageEnglish
Article number064710
Pages1 - 14
Number of pages14
JournalJournal of Chemical Physics
Volume143
Issue number6
DOIs
StatusPublished - 14 Aug 2015

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Lattice vibrations
functionals
harmonics
Chalcogenides
chalcogenides
Local density approximation
Temperature
approximation
Lattice constants
Specific heat
Thermal expansion
Zinc
Materials properties
gradients
Elastic moduli
Semiconductor materials
bulk modulus
temperature
II-VI semiconductors
thermal expansion

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Influence of the exchange-correlation functional on the quasi-harmonic lattice dynamics of II-VI semiconductors. / Skelton, Jonathan M.; Tiana, Davide; Parker, Stephen C.; Togo, Atsushi; Tanaka, Isao; Walsh, Aron.

In: Journal of Chemical Physics, Vol. 143, No. 6, 064710, 14.08.2015, p. 1 - 14.

Research output: Contribution to journalArticle

Skelton, Jonathan M. ; Tiana, Davide ; Parker, Stephen C. ; Togo, Atsushi ; Tanaka, Isao ; Walsh, Aron. / Influence of the exchange-correlation functional on the quasi-harmonic lattice dynamics of II-VI semiconductors. In: Journal of Chemical Physics. 2015 ; Vol. 143, No. 6. pp. 1 - 14
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