Accurate Simulation of Spectroscopic Signatures of Cavity-Assisted, Conical-Intersection-Controlled Singlet Fission Processes.

A numerically accurate, fully quantum methodology has been developed for the simulation of the dynamics and nonlinear spectroscopic signals of cavity-assisted, conical-intersection-controlled singlet fission systems. The methodology is capable of handling several molecular systems strongly coupled to the photonic mode of the cavity and treats the intrinsic conical intersection and cavity-induced polaritonic conical intersections in a numerically exact manner. Contributions of higher-lying molecular electronic states are accounted for comprehensively. The intriguing process of cavity-modified fission dynamics, including all of its electronic, vibrational, and photonic degrees of freedom, together with its two-dimensional spectroscopic manifestation, is simulated for two rubrene dimers strongly coupled to the cavity mode.