Monte Carlo simulations of crystal defects in open ensembles

Abstract: Open materials systems are often inaccessible to conventional atomistic simulations, which add and remove atoms by creating high-energy defects that may be sampled with vanishing probability. This longstanding challenge motivates a new Hamiltonian Monte Carlo method that maps the grand canonical problem to a canonical system involving non-interacting fictitious particles. To trial deletions or insertions, a real or fictitious particle is selected according to an energy-based biasing scheme and gradually transformed over a microcanonical molecular dynamics trajectory. The method is validated, optimized, and used to compute point defect free energies that allow for arbitrary structures and interactions among multiple defects. Several grain boundaries are then equilibrated in a physically representative open ensemble, demonstrating a new approach to studying interface structures and their phase transitions.