Four-electron model for singlet and triplet excitation energy transfers with inclusion of coherence memory, inelastic tunneling and nuclear quantum effects

•Theoretical scheme to describe the coherent dynamics of excitation energy transfer is proposed.•Four-electron model is employed to consider both of singlet and triplet excitation energy transfers.•Physical effects such as coherence memory, inelastic tunneling and quantum feature of phonon are taken into account.•Test calculations are performed to study the dependence on relevant physical parameters.

A computational scheme to describe the coherent dynamics of excitation energy transfer (EET) in molecular systems is proposed on the basis of generalized master equations with memory kernels. This formalism takes into account those physical effects in electron-bath coupling system such as the spin symmetry of excitons, the inelastic electron tunneling and the quantum features of nuclear motions, thus providing a theoretical framework to perform an ab initio description of EET through molecular simulations for evaluating the spectral density and the temporal correlation function of electronic coupling. Some test calculations have then been carried out to investigate the dependence of exciton population dynamics on coherence memory, inelastic tunneling correlation time, magnitude of electronic coupling, quantum correction to temporal correlation function, reorganization energy and energy gap.

Graphical abstractDownload high-res image (146KB)Download full-size image