Dynamical outcomes of quenching: Reflections on a conical intersection

Abstract

This review focuses on experimental studies of the dynamical outcomes following collisional quenching of electronically excited OH A 2Σ+} radicals by molecular partners. The experimental observables include the branching between reactive and nonreactive decay channels, kinetic energy release, and quantum state distributions of the products. Complementary theoretical investigations reveal regions of strong nonadiabatic coupling, known as conical intersections, which facilitate the quenching process. The dynamical outcomes observed experimentally are connected to the local forces and geometric properties of the nuclei in the conical intersection region. Dynamical calculations for the benchmark OH-H2 system are in good accord with experimental observations, demonstrating that the outcomes reflect the strong coupling in the conical intersection region as the system evolves from the excited electronic state to quenched products. Copyright © 2014 by Annual Reviews.