Exact Wave Packet Dynamics of Singlet Fission in Unsubstituted and Substituted Polyene Chains within Long-Range Interacting Models

Abstract

Singlet fission is a potential pathway for significant enhancement of efficiency in organic solar cells. In this article, we have studied singlet fission in a pair of polyene molecules employing exact many-body wave packet dynamics. The individual molecules are treated within Hubbard and Pariser-Parr-Pople (PPP) models and the interaction between them involves transfer terms, intersite electron repulsions and site charge-bond charge repulsion terms. Initial wave packet is constructed from excited singlet state of one molecule and ground state of the other. Time development of this wave packet under the influence of intermolecular interactions is followed within the Schr\"{o}dinger picture by an efficient predictor-corrector scheme. In unsubstituted Hubbard and PPP chains, $2{}^1A$ excited singlet state leads to significant fission yield while the $1{}^1B$ state gives negligible fission yield. On substitution by donor-acceptor groups of moderate strength, singlet state derived from $1{}^1B$ state also gives significant fission yield within PPP model. Furthermore, we find the fission yield depends considerably on the stacking arrangement of the polyene molecules.