A novel conical intersection topography and its consequences: The 1, 2A2 conical intersection seam of the vinoxy radical

Abstract

A region of the 1, 2 2A seam of accidental conical intersections in the vinoxy radical exhibits a novel topography which has important consequences for both upper-state to lower-state and lower-state to upper-state nonadiabatic transitions. The impact of this topography on these nonadiabatic transitions is described. We also considered the possibility that this conical intersection seam provides a dynamical bottleneck to the photodissociation of vinoxy to H+ketene by facilitating nonadiabatic recrossing. Our analysis of the conical topographies and the proximity of the conical intersections to the transition state for dissociation to H+ketene does not support nonadiabatic recrossing as an effective dynamical bottleneck blocking the H+ketene channel.