Role of the Dark 2Ag State in Donor-Acceptor Copolymers as a Pathway for Singlet Fission: A DMRG Study

The mechanism of intramolecular singlet fission in donor acceptor-type copolymers, especially the role of the dark 2A(g) state, is not so clear. In this Letter, the is electronic structure of the benzodithiophene (B-thiophene-1,1-dioxide (TDO) copolymer is calculated by density matrix renormalization group theory with the Pariser Parr Pople model. We find that the dark 2A(g) state is the lowest singlet excited state and is nearly degenerate with the 1B(u) state. So, a fast internal conversion from 1B(u) to 2A(g) state is highly possible. The 2A(g) state has a strong triplet pair character, localized on two neighboring acceptor units, which indicates that it is an intermediate state for the intramolecular singlet fission process. With the increase of the donor acceptor push pull strength in our model, this triplet pair character of the 2A(g) state becomes more prominent, and meanwhile the binding energy of this coupled triplet pair state decreases, which favors the separation into two uncoupled triplet states. We propose a model in which the competition between the singlet fission process and the nonradiative decay process from the 2A(g) state would determine the final quantum yield.