Exploring Isomerization Dynamics on a Potential Energy Surface with an Index-2 Saddle using Lagrangian Descriptors (2001.11049v1)

Abstract: In this paper we explore the phase space structures governing isomerization dynamics on a potential energy surface with four wells and an index-2 saddle. For this model, we analyze the influence that coupling both degrees of freedom of the system and breaking the symmetry of the problem have on the geometrical template of phase space structures that characterizes reaction. To achieve this goal we apply the method of Lagrangian descriptors, a technique with the capability of unveiling the key invariant manifolds that determine transport processes in nonlinear dynamical systems. This approach reveals with extraordinary detail the intricate geometry of the isomerization routes interconnecting the different potential wells, and provides us with valuable information to distinguish between initial conditions that undergo sequential and concerted isomerization.