Photo‐induced energy and charge transfer dynamics in Y6 dimers

Abstract Y6 (BTP‐4F) is one of the novel non‐fullerene acceptors and its photo‐physics significantly affects the efficiency of organic solar cells. Here, the photo‐induced energy and charge transfer (CT) dynamics in four typical dimers (Y, C, S1, and S2)‐TYPE from Y6 films are revealed by combining electronic structure theory calculations, rate theories, and quantum dynamics simulations. The rate theories show that in ground‐state CT processes the Y‐TYPE is bipolar with the largest rate among all dimers, and in excitation energy transfer the triplet rates are about 10 5 smaller than the singlet ones, however, the singlet rates can reach 10 13 s −1 , which may lead to the rate theories invalid. The stochastic Schrödinger equation based on the diabatic Hamiltonian is thus adopted to reveal excited‐state dynamics. The results show that three of the four dimers are H‐aggregate except for S1‐TYPE with J‐aggregate property. However, these J/H‐aggregate properties are excited‐state dependent, for instance, the Y‐TYPE becomes J‐aggregate in the second excited‐state. Furthermore, CT states are strongly mixed with the first two excited states, which can dramatically impact the energy transfer. Indeed, the dynamic simulations clarify that the excited‐state energy relaxation mediated by CT states can be performed in the first 20 fs, and the CT‐state population is even non‐negligible in the quasi‐stationary distribution.