Structure, rearrangements and evaporation of rotating atomic clusters

Abstract

Eigenvector-following techniques are used to explore the classical effective potential energy surface of rotating clusters composed of identical rare gas atoms. Precise determination of transition states reveals the mechanisms for atomic rearrangements and allows us to calculate rate constants for the evaporation of an atom from the cluster surface using RRK theory. We examine the variation in the effective potential energy surface with the magnitude of the angular momentum, with particular reference to centrifugal distortion and the resulting spectroscopic constants, the Hessian index of the stationary points, and the centrifugal barriers to evaporation. Most of the calculations are performed using a pairwise additive Lennard-Jones potential, but comparisons are made with the accurate Aziz potential augmented by a three-body Axilrod-Teller term.