Theoretical Studies of Singlet Fission: Searching for Materials and Exploring Mechanisms

In this Review article, a survey is given for theoretical studies in the subject of singlet fission. Singlet fission converts one singlet exciton to two triplet excitons. With the doubled number of excitons and the longer lifetime of the triplets, singlet fission provides an avenue to improve the photoelectric conversion efficiency in organic photovoltaic devices. It has been a subject of intense research in the past decade. Theoretical studies play an essential role in understanding singlet fission. This article presents a Review of theoretical studies in singlet fission since 2006, the year when the research interest in this subject was reignited. Both electronic structure and dynamics studies are covered. Electronic structure studies provide guidelines for designing singlet fission chromophores and insights into the couplings between single‐ and multi‐excitonic states. The latter provides fundamental knowledge for engineering interchromophore conformations to enhance the fission efficiency. Dynamics studies reveal the importance of vibronic couplings in singlet fission

Identifying (BN)2-pyrene as a new class of singlet fission chromophores: significance of azaborine substitution

Singlet fission converts one photoexcited singlet state to two triplet excited states and raises photoelectric conversion efficiency in photovoltaic devices. However, only a handful of chromophores have been known to undergo this process, which greatly limits the application of singlet fission in photovoltaics. We hereby identify a recently synthesized diazadiborine-pyrene ((BN)2-pyrene) as a singlet fission chromophore. Theoretical calculations indicate that it satisfies the thermodynamics criteria for singlet fission. More importantly, the calculations provide a physical chemistry insight into how the BN substitution makes this happen. Both calculation and transient absorption spectroscopy experiment indicate that the chromophore has a better absorption than pentacene. The convenient synthesis pathway of the (BN)2-pyrene suggests an in situ chromophore generation in photovoltaic devices. Two more (BN)2-pyrene isomers are proposed as singlet fission chromophores. This study sets a step forward in the cross-link of singlet fission and azaborine chemistry

Design of Small Intramolecular Singlet Fission Chromophore: An Azaborine Candidate and General Small Size Effects

We report the first attempt to design small intramolecular singlet fission chromophores, with the aid of quantum chemistry and explicitly simulating the time evolution of state populations using quantum dynamics method. We start with three previously proposed azaborine-substituted intermolecular singlet fission chromophores. Through analyzing their frontier orbital amplitudes, we select a BN-substituted azulene as the building block. Covalently connecting two such monomers and tuning their relative configuration, we examine three dimers. One dimer is found to be an eminent candidate: the triplet-pair state is quickly formed within 1 ps, and the two triplets are ready to be disentangled. We elucidate the general small size effects in intramolecular singlet fission and focus on specific aspects which should be taken care of when manipulating the fission rate through steric hindrance

Origins of singlet fission in solid pentacene from an ab initio Green's-function approach

We develop a new first-principles approach to predict and understand rates of singlet fission with an ab initio Green's-function formalism based on many-body perturbation theory. Starting with singlet and triplet excitons computed from a GW plus Bethe-Salpeter equation approach, we calculate the exciton--bi-exciton coupling to lowest order in the Coulomb interaction, assuming a final state consisting of two non-interacting spin-correlated triplets with finite center-of-mass momentum. For crystalline pentacene, symmetries dictate that the only purely Coulombic fission decay from a bright singlet state requires a final state consisting of two inequivalent nearly degenerate triplets of nonzero, equal and opposite, center-of-mass momenta. For such a process, we predict a singlet lifetime of 40 to 150 fs, in very good agreement with experimental data, indicating that this process can dominate singlet fission in crystalline pentacene. Our approach is general and provides a framework for predicting and understanding multiexciton interactions in solids

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

Singlet fission (SF) is a potential pathway for significant enhancement of efficiency in organic solar cells (OSC). In this paper, we study singlet fission in a pair of polyene molecules in two different stacking arrangements employing exact many-body wave packet dynamics. In the non-interacting model, the SF yield is absent. 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\"odinger picture by an efficient predictor-corrector scheme. In unsubstituted Hubbard and PPP chains, $2{}^1A$ excited singlet state leads to significant SF yield while the $1{}^1B$ state gives negligible fission yield. On substitution by donor-acceptor groups of moderate strength, the lowest excited state will have sufficient $2{}^1A$ character and hence results in significant SF yield. Because of rapid internal conversion, the nature of the lowest excited singlet will determine the SF contribution to OSC efficiency. Furthermore, we find the fission yield depends considerably on the stacking arrangement of the polyene molecules.Comment: 13 pages, 8 figures, 4 table

Design of singlet fission chromophores with cyclic (alkyl)(amino) carbene building blocks

We use MRSF-TDDFT and NEVPT2 methods to design singlet fission chromophores with the building blocks of cyclic (alkyl)(amino)carbenes (CAACs). CAAC dimers with C2, C4, and p-phenylene spacers are considered. The substitutions with trifluoromethyls and fluorine atoms at the α C position are investigated. The electronegative substituents enhance the π accepting capability of the α C, while maintaining it as a quaternary C atom. The phenylene-connected dimers with the two substitutions are identified as promising candidates for singlet fission chromophores. The cylindrically symmetric C2 and C4 spacers allow for substantial structural reorganizations in the S0-to-S1 and S0-to-T1 excitations. Although the two substituted dimers with the C4 spacer satisfy (or very close to satisfy) the primary thermodynamics criterion for singlet fission, the significant structural reorganizations result in high barriers so that the fission is kinetically unfavorable