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Updated: Feb 18, 2026

Excitonic Hamiltonians for Calculating Optical Absorption Spectra and Optoelectronic Properties of Molecular Aggregates and Solids
Published on: May 27, 2020
Construction of Vibronic Diabatic Hamiltonian for Excited-State Electron and Energy Transfer Processes
Yu Xie1, Shengshi Jiang1,2, Jie Zheng3
1CAS Key Laboratory of Biobased Materials, Qingdao Institute of Bioenergy and Bioprocess Technology, Chinese Academy of Sciences , Qingdao 266101, China.
Abstract:
Photoinduced excited-state electron and energy transfer processes are crucial in biological photoharvesting systems and organic photovoltaic devices. We discuss the construction of a diabatic vibronic Hamiltonian for the proper treatment of these processes involving the projection approach acting on both electronic wave functions and vibrational modes. In the electronic part, the wave function projection approach is used to construct the diabatic Hamiltonian in which both local excited states and charge-transfer states are included on the same footing. For the vibrational degrees of freedom, the vibronic couplings in the diabatic Hamiltonian are obtained in the basis of the pseudonormal modes localized on each monomer site by applying delocalized-to-localized mode projection. This systematic approach allows us to construct the vibronic diabatic Hamiltonian in molecular aggregates.
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