Optical-cavity manipulation strategies of singlet fission systems mediated by conical intersections: Insights from fully quantum simulations

We offer a theoretical perspective on simulation and engineering of polaritonic conical-intersection-driven singlet-fission (SF) materials. We begin by examining fundamental models, including Tavis–Cummings and Holstein–Tavis–Cummings Hamiltonians, exploring how disorder, non-Hermitian effects, and finite temperature conditions impact their dynamics, setting the stage for studying conical intersections and their crucial role in SF. Using rubrene as an example and applying the numerically accurate Davydov Ansatz methodology, we derive dynamic and spectroscopic responses of the system and demonstrate key mechanisms capable of SF manipulation, viz. cavity-induced enhancement/weakening/suppression of SF, population localization on the singlet state via engineering cavity-mode excitation, polaron/polariton decoupling, and collective enhancement of SF. We outline unsolved problems and challenges in the field and share our views on the development of the future lines of research. We emphasize the significance of careful modeling of cascades of polaritonic conical intersections in high excitation manifolds and envisage that collective geometric phase effects may remarkably affect the SF dynamics and yield. We argue that the microscopic interpretation of the main regulatory mechanisms of polaritonic conical-intersection-driven SF can substantially deepen our understanding of this process, thereby providing novel ideas and solutions for improving conversion efficiency in photovoltaics.