Signatures of a Conical Intersection in Adiabatic Dissociation on the Ground Electronic State

Abstract

Conical intersections are known to cause nonadiabatic transitions, but their effects on adiabatic dynamics are often ignored. Using the overtone-induced dissociation of the hydroxymethyl radical as an example, we demonstrate that ground-state O-H bond rupture is significantly affected by a conical intersection with an electronically excited state along the dissociation path, despite the much lower energy of the dissociating state than that of the conical intersection. In addition to lifetime differences, the geometric phase leads to a different H₂CO rotational state distribution compared with that obtained using the standard single-state adiabatic model, which constitutes a signature of the conical intersection.