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

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

Revisiting the (E + A) ⊗ (e + a) problems of polyatomic systems with trigonal symmetry: general expansions of their vibronic Hamiltonians

In this work, we derive general expansions in vibrational coordinates for the (E + A) ⊗ (e + a) vibronic Hamiltonians of molecules with one and only one C3 axis. We first derive the expansion for the lowest C3 symmetry. Additional symmetry elements systematically eliminate terms in the expansion. We compare our expansions with the previous results for two cases, the Image ID:c7cp01171g-t73.gif and the C3 (E + A) ⊗ e. The first comparison demonstrates the robustness, completeness, conciseness, and convenience of our formalism. There is a systematic discrepancy in the second comparison. We discuss the origin of the discrepancy and use a numerical example to corroborate our expansion. Our formalism covers 153 vibronic problems in 6 point groups. It also gives general expansions for the spin–orbit vibronic Hamiltonians of the p-type (E + A) ⊗ (e + a) problems

Well-Posedness for the Motion of Physical Vacuum of the Three-dimensional Compressible Euler Equations with or without Self-Gravitation

This paper concerns the well-posedness theory of the motion of physical vacuum for the compressible Euler equations with or without self-gravitation. First, a general uniqueness theorem of classical solutions is proved for the three dimensional general motion. Second, for the spherically symmetric motions, without imposing the compatibility condition of the first derivative being zero at the center of symmetry, a new local-in-time existence theory is established in a functional space involving less derivatives than those constructed for three-dimensional motions in \cite{10',7,16'} by constructing suitable weights and cutoff functions featuring the behavior of solutions near both the center of the symmetry and the moving vacuum boundary.Comment: To appear in Arch. Rational Mech. Ana