CASM Monte Carlo: Calculations of the thermodynamic and kinetic properties of complex multicomponent crystals

TL;DR

This paper introduces Monte Carlo techniques within the CASM software to analyze thermodynamic and kinetic properties of complex multicomponent crystals, including phase diagrams and phase transitions.

Contribution

It presents a new framework and software tools for modeling complex crystal structures with multiple species and vacancies using Monte Carlo methods.

Findings

Successful calculation of free energies and kinetic coefficients.

Demonstration of phase transition analysis in complex crystals.

Development of casm-flow for automating simulations.

Abstract

Monte Carlo techniques play a central role in statistical mechanics approaches for connecting macroscopic thermodynamic and kinetic properties to the electronic structure of a material. This paper describes the implementation of Monte Carlo techniques for the study multicomponent crystalline materials within the Clusters Approach to Statistical Mechanics (CASM) software suite, and demonstrates their use in model systems to calculate free energies and kinetic coefficients, study phase transitions, and construct first-principles based phase diagrams. Many crystal structures are complex, with multiple sublattices occupied by differing sets of chemical species, along with the presence of vacancies or interstitial species. This imposes constraints on concentration variables, the form of thermodynamic potentials, and the values of kinetic transport coefficients. The framework used by CASM to formulate thermodynamic potentials and kinetic transport coefficients accounting for arbitrarily complex crystal structures is presented and demonstrated with examples applying it to crystal systems of increasing complexity. Additionally, a new software package is introduced, casm-flow, which helps automate the setup, submission, management, and analysis of Monte Carlo simulations performed using CASM.