Chaotic dynamics near steep transition states

Abstract

Classical molecular motion near potential energy saddles can be more or less chaotic relative to motion near minima. The relative degree of chaos depends on the extent of coupling between the degrees of freedom and on the curvature of the potential energy landscape. Here, we explore these effects using constant energy molecular dynamics simulations and independent criteria associated with locally chaotic behavior – namely, the constancy of the local mode action and the magnitude of finite-time Lyapunov exponents. These criteria reconcile the chaotic basins and relatively ordered saddles of the Lennard-Jones trimer, with the chaotic saddles and ordered basins for reactive, all-atom H2O described by the Garofalini H2O potential. By modifying the Garofalini and Lennard-Jones models we separate the compounding effects of nonlinear three-body interactions and steep reaction path curvature on the local degree of chaos near saddles and minima.