Triplet‐triplet Annihilation Dynamics of Naphthalene

Abstract Triplet‐triplet annihilation (TTA) is a spin‐allowed conversion of two triplet states into one singlet excited state, which provides an efficient route to generate a photon of higher frequency than the incident light. Multiple energy transfer steps between absorbing (sensitizer) and emitting (annihilator) molecular species are involved in the TTA based photon upconversion process. TTA compounds have recently been studied for solar energy applications, even though the maximum upconversion efficiency of 50 % is yet to be achieved. With the aid of quantum calculations and based on a few key requirements, several design principles have been established to develop the well‐functioning annihilators. However, a complete molecular level understanding of triplet fusion dynamics is still missing. In this work, we have employed multi‐reference electronic structure methods along with quantum dynamics to obtain a detailed and fundamental understanding of TTA mechanism in naphthalene. Our results suggest that the TTA process in naphthalene is mediated by conical intersections. In addition, we have explored the triplet fusion dynamics under the influence of strong light‐matter coupling and found an increase of the TTA based upconversion efficiency.