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Excimer Energies.

Ruoqi ZhaoChristian HettichJun ZhangMeiyi LiuJiali Gao
Published in: The journal of physical chemistry letters (2023)
A multistate energy decomposition analysis (MS-EDA) method is introduced for excimers using density functional theory. Although EDA has been widely applied to intermolecular interactions in the ground state, few methods are currently available for excited-state complexes. Here, the total energy of an excimer state is separated into exciton excitation energy Δ E Ex (|Ψ X ·Ψ Y ⟩*), resulting from the state interaction between locally excited monomer states |Ψ X * ·Ψ Y ⟩ and |Ψ X ·Ψ Y * ⟩ , a superexchange stabilization energy Δ E SE , originating from the mutual charge transfer between two monomers |Ψ X + ·Ψ Y ⟩ and |Ψ X - ·Ψ Y + ⟩ , and an orbital-and-configuration delocalization term Δ E OCD due to the expansion of configuration space and block-localized orbitals to the fully delocalized dimer system. Although there is no net charge transfer in symmetric excimer cases, the resonance of charge-transfer states is critical to stabilizing the excimer. The monomer localized excited and charge-transfer states are variationally optimized, forming a minimal active space for nonorthogonal state interaction (NOSI) calculations in multistate density functional theory to yield the intermediate states for energy analysis. The present MS-EDA method focuses on properties unique to excited states, providing insights into exciton coupling, superexchange and delocalization energies. MS-EDA is illustrated on the acetone and pentacene excimer systems; three configurations of the latter case are examined, including the optimized excimer, a stacked configuration of two pentacene molecules and the fishbone orientation. It is found that excited-state energy splitting is strongly dependent on the relative energies of the monomer excited states and the phase-matching of the monomer wave functions.
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