Computing classically exact diffusion constants using short-time trajectories

Abstract

The classical diffusion constant of a point defect in an infinite lattice of binding sites is shown to be expressible as transition-state-theory rates multiplied by dynamical correction factors computed from short-time classical trajectories initiated at the site boundaries. The expression, which results from time differentiating the lattice-discretized mean-square displacement, is valid at any temperature for which the site lattice is well defined. It thus avoids both the time-scale limitations of direct molecular dynamics and the rare-event requirements of standard dynamical-correction methods.