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Mechanism of Spin-Exchange Internal Conversion: Practical Proxies for Diabatic and Nonadiabatic Couplings

Abstract : Spin-exchange internal conversion (SEIC) is a general class of reactions having singlet fission and triplet fusion as particular cases. Based on a charge-transfer (CT)-mediated mechanism and analytical derivation with a model Hamiltonian, we propose proxies for estimating the coupling strength in both diabatic and adiabatic pictures for general SEIC reactions. In the diabatic picture, we demonstrated the existence of a bilinear relationship between the coupling strength and molecular orbital overlap , which provides a practical way to predict diabatic couplings. In the adiabatic picture, we showed that nonadiabatic couplings can be approximated by simple functions of the wave function CT coefficients. These approaches were verified through the investigation of singlet oxygen photosensitization, where both 1 Δg and 1 g oxygen states can be competitively generated by a triplet fusion reaction. The interplay between the CT-mediated mechanism, the spatial factors of the bimolecular complex, and the electronic structure of the oxygen molecule during the reaction explains the curiously small coupling to the 1 g state along specific incidence directions. The results from both the diabatic and adiabatic pictures provide a comprehensive understanding of the reaction mechanism, which applies to general SEIC problems.
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Shuming Bai, Mario Barbatti. Mechanism of Spin-Exchange Internal Conversion: Practical Proxies for Diabatic and Nonadiabatic Couplings. Journal of Chemical Theory and Computation, American Chemical Society, 2019, 15 (3), pp.1503-1513. ⟨10.1021/acs.jctc.8b00923⟩. ⟨hal-02288617⟩

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