Surface self‐diffusion constants were calculated for the single component Lennard‐Jones face-centered cubic(111) system using the dynamical corrections formalism for transition state theory. At high temperatures, these results were found to be in agreement with previous molecular dynamics calculations. Over the extended temperature range in which this method was valid, deviations from Arrhenius behavior were observed. At lower temperatures, a noticeable contribution to the diffusion constant stems from trajectories in which the adatom re-crosses the transition state theory boundary, often due to a direction‐reversing collision with the substrate atom on the far side of the binding site. This produced a dip in the dynamical correction factor centered around a reduced temperature of 0.038. At higher temperatures, the expected multiple‐jump effects were observed.

Self-Diffusion on the Lennard-Jones FCC(111) Surface: Effects of Temperature on Dynamical Corrections. Cohen, J.M., Voter, A.F.: Journal of Chemical Physics, 1989, 91, 5082