Vibrational free energy and phase stability of paramagnetic and antiferromagnetic CrN from ab-initio molecular dynamics

Abstract

We present a theoretical first-principles method to calculate the free energy of a magnetic system in its high-temperature paramagnetic phase, including vibrational, electronic, and magnetic contributions. The method for calculating free energies is based on ab-initio molecular dynamics and combines a treatment of disordered magnetism using disordered local moments molecular dynamics (DLM-MD) with the temperature dependent effective potential (TDEP) method to obtain the vibrational contribution to the free energy. We illustrate the applicability of the method by obtaining the anharmonic free energy for the paramagnetic cubic and the antiferromagnetic orthorhombic phases of chromium nitride. The influence of lattice dynamics on the transition between the two phases is demonstrated by constructing the temperature-pressure phase diagram.