A truncated quasiharmonic method for free energy calculations and finite-temperature applications

Abstract

Harmonic-based finite-temperature calculation methods play an important role in the study of thermodynamic properties of materials. In this study, we propose a truncated quasiharmonic (TQH) method to approximate the Helmholtz free energy by truncating the high-order terms of finite-temperature vibrational energy. To evaluate the efficacy of the TQH method against other established finite-temperature methods, i.e. the quasiharmonic (QH), the modified local harmonic (MLH) and the local quasiharmonic (LQH) methods, analysis of a homogeneous and vacancy-containing atomic system is performed with each method and compared. We found that the TQH method provides improved accuracy over the MLH and LQH methods for a system containing defects while requiring less computational time than the QH method to achieve convergence.