Anisotropic temperature-dependent lattice parameters and elastic constants from first principles

Abstract

The Quasi-harmonic Approximation (QHA) is a widely used method for calculating the temperature dependence of lattice parameters and the thermal expansion coefficients from first principles. However, applying QHA to anisotropic systems typically requires several dozens or even hundreds of phonon band structure calculations, leading to high computational costs. The Zero Static Internal Stress Approximation (ZSISA) QHA method partly addresses such caveat, but the computational load of its implementation remains high, so that its volumetric-only counterpart v-ZSISA-QHA is preferred. In this work, we present an efficient implementation of the ZSISA-QHA, enabling its application across a wide range of crystal structures under varying temperature (T) and pressure (P) conditions. By incorporating second-order derivatives of the vibrational free energy with respect to lattice degrees of freedom, we significantly reduce the number of required phonon band structure calculations for the determination of all lattice parameters and angles. For hexagonal, trigonal, and tetragonal systems, only six phonon band structure calculations are needed, while 10, 15, and 28 calculations suffice for orthorhombic, monoclinic, and triclinic systems, respectively. This method is tested for a variety of non-cubic materials, from uniaxial ones like ZnO and CaCO3 to monoclinic or triclinic materials such as ZrO2, HfO2, and Al2SiO5, demonstrating a significant reduction in computational effort while maintaining accuracy in modeling anisotropic thermal expansion, unlike the v-ZSISA-QHA. The method is also applied to the first-principles calculation of temperature-dependent elastic constants, with only up to six more phonon band structure calculations, depending on the crystallographic system.