Coherent singlet fission activated by symmetry breaking

Nat Chem. 2017 Oct;9(10):983-989. doi: 10.1038/nchem.2784. Epub 2017 May 29.

Abstract

Singlet fission, in which a singlet exciton is converted to two triplet excitons, is a process that could be beneficial in photovoltaic applications. A full understanding of the dynamics of singlet fission in molecular systems requires detailed knowledge of the relevant potential energy surfaces and their (conical) intersections. However, obtaining such information is a nontrivial task, particularly for molecular aggregates. Here we investigate singlet fission in rubrene crystals using transient absorption spectroscopy and state-of-the-art quantum chemical calculations. We observe a coherent and ultrafast singlet-fission channel as well as the well-known and conventional thermally assisted incoherent channel. This coherent channel is accessible because the conical intersection for singlet fission on the excited-state potential energy surface is located very close to the equilibrium position of the ground-state potential energy surface and also because of the excitation of an intermolecular symmetry-breaking mode, which activates the electronic coupling necessary for singlet fission.

Publication types

  • Research Support, Non-U.S. Gov't