On how differently the quasi-harmonic approximation works for two isostructural crystals: Thermal properties of periclase and lime
- Dipartimento di Chimica, Università di Torino and NIS, Nanostructured Interfaces and Surfaces, Centre of Excellence, Via Giuria 5, 10125 Torino (Italy)
- Physics Department, Faculty of Science, Razi University, Kermanshah (Iran, Islamic Republic of)
Harmonic and quasi-harmonic thermal properties of two isostructural simple oxides (periclase, MgO, and lime, CaO) are computed with ab initio periodic simulations based on the density-functional-theory (DFT). The more polarizable character of calcium with respect to magnesium cations is found to dramatically affect the validity domain of the quasi-harmonic approximation that, for thermal structural properties (such as temperature dependence of volume, V(T), bulk modulus, K(T), and thermal expansion coefficient, α(T)), reduces from [0 K-1000 K] for MgO to just [0 K-100 K] for CaO. On the contrary, thermodynamic properties (such as entropy, S(T), and constant-volume specific heat, C{sub V}(T)) are described reliably at least up to 2000 K and quasi-harmonic constant-pressure specific heat, C{sub P}(T), up to about 1000 K in both cases. The effect of the adopted approximation to the exchange-correlation functional of the DFT is here explicitly investigated by considering five different expressions of three different classes (local-density approximation, generalized-gradient approximation, and hybrids). Computed harmonic thermodynamic properties are found to be almost independent of the adopted functional, whereas quasi-harmonic structural properties are more affected by the choice of the functional, with differences that increase as the system becomes softer.
- OSTI ID:
- 22416040
- Journal Information:
- Journal of Chemical Physics, Vol. 142, Issue 4; Other Information: (c) 2015 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA); ISSN 0021-9606
- Country of Publication:
- United States
- Language:
- English
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