A systematic model study quantifying how conical intersection topography modulates photochemical reactions

Abstract

Despite their important role in photochemistry and expected presence in most polyatomic molecules, conical intersections have been thoroughly characterized in a comparatively small number of systems. Conical intersections can confer molecular photoreactivity or photostability, often with remarkable efficacy, due to their unique structure: at a conical intersection, the adiabatic potential energy surfaces of two or more electronic states are degenerate, enabling ultrafast decay from an excited state without radiative emission, known as nonadiabatic transfer. Furthermore, the precise conical intersection topography determines fundamental properties of photochemical processes, including excited-state decay rate, efficacy, and molecular products that are formed. However, these relationships have yet to be defined comprehensively. In this article, we use an adaptable computational model to investigate a variety of conical intersection topographies, simulate resulting nonadiabatic dynamics, and calculate key photochemical observables. We varied the vibrational mode frequencies to modify conical intersection topography systematically in four primary classes of conical intersections and quantified the resulting rate, total yield, and product yield of nonadiabatic decay. The results reveal that higher vibrational mode frequencies reduce nonadiabatic transfer, but increase the transfer rate and resulting photoproduct formation. These trends can inform progress toward experimental control of photochemical reactions or tuning of molecules’ photochemical properties based on conical intersections and their topography.