Assessment of Approximate Methods for Anharmonic Free Energies

• DOI: 10.1021/acs.jctc.9b00596
• Publication Date: 2019-09-18T21:17:44Z
• Authors: Venkat Kapil; Edgar Engel; Mariana Rossi; Michele Ceriotti
• Keywords: Condensed Matter - Materials Science; Statistical Mechanics (cond-mat.stat-mech); 0103 physical sciences; Materials Science (cond-mat.mtrl-sci); FOS: Physical sciences; 01 natural sciences; Condensed Matter - Statistical Mechanics

Quantitative evaluations of the free energy of materials must take into account thermal and zero-point energy fluctuations. While these effects can easily be estimated within a harmonic approximation, corrections arising from the anharmonic nature of the interatomic potential are often crucial and require computationally costly path integral simulations. Consequently, different approximate frameworks for computing affordable estimates of the anharmonic free energies have been developed over the years. Understanding which of the approximations involved are justified for a given system is complicated by the lack of comparative benchmarks. To facilitate this choice we assess the accuracy and efficiency of some of the commonly used approximate methods -- the vibrational self-consistent field and self-consistent phonons -- by comparing the anharmonic correction to the Helmholtz free energy against reference path integral calculations. These benchmarks are performed for a diverse set of systems, ranging from simple quasi-harmonic solids to flexible molecular crystals with freely-rotating units. Our results suggest that for simple solids such as allotropes of carbon these methods yield results that are in excellent agreement with the reference calculations, at a considerably lower computational cost. For more complex molecular systems such as polymorphs of ice and paracetamol the methods do not consistently provide a reliable approximation of the anharmonic correction. Despite substantial cancellation of errors when comparing the stability of different phases, we do not observe a systematic improvement over the harmonic approximation even for relative free-energies. Our results suggest that efforts towards obtaining computationally-feasible anharmonic free-energies for flexible molecular solids should therefore be directed towards reducing the expense of path integral methods