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Updated: Apr 28, 2026

Excitonic Hamiltonians for Calculating Optical Absorption Spectra and Optoelectronic Properties of Molecular Aggregates and Solids
Published on: May 27, 2020
Energy relaxation and separation of a hot electron-hole pair in organic aggregates from a time-dependent wavepacket
Lu Han1, Xinxin Zhong1, WanZhen Liang1
1State Key Laboratory of Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Materials, Fujian Provincial Key Lab of Theoretical and Computational Chemistry, and Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, People's Republic of China.
Abstract:
The time-dependent wavepacket diffusive method [X. Zhong and Y. Zhao, J. Chem. Phys. 138, 014111 (2013)] is extended to investigate the energy relaxation and separation of a hot electron-hole pair in organic aggregates with incorporation of Coulomb interaction and electron-phonon coupling. The pair initial condition generated by laser pulse is represented by a Gaussian wavepacket with a central momentum. The results reveal that the hot electron energy relaxation is very well described by two rate processes with the fast rate much larger than the slow one, consistent with experimental observations, and an efficient electron-hole separation is accomplished accompanying the fast energy relaxation. Furthermore, although the extra energy indeed helps the separation by overcoming the Coulomb interaction, the width of initial wavepacket is much sensitive to the separation efficiency and the narrower wavepacket generates the more separated charges. This behavior may be useful to understand the experimental controversy of the hot carrier effect on charge separation.
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