Using multistate dynamical corrections to compute classically exact diffusion constants at arbitrary temperature

Abstract

A method is presented for computing the classically exact, surface or bulk diffusion constant of a point defect at arbitrary temperature. The thermal diffusion constant is expressed using the squared jump length averaged over all possible final states to which the atom can jump. The rate constants that weight this sum are computed using transition state theory and molecular dynamics within a recently developed many-state dynamical corrections formalism. While these rate constants are valid only in the rare-event regime (i.e., at low temperature), it is shown that for a periodic lattice of equivalent binding sites, the resulting diffusion contants is valid at any temperature for which the lattice sites remain well defined. It is thus possible to compute classically exact surface or bulk diffusion constant for an arbitrary interatomic potential, without the time scale limitations of direct molecular dynamics.