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Real‐time Simulations of Photoinduced Coherent Charge Transfer and Proton‐Coupled Electron Transfer
Author(s) -
Eisenmayer Thomas J.,
Buda Francesco
Publication year - 2014
Publication title -
chemphyschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.016
H-Index - 140
eISSN - 1439-7641
pISSN - 1439-4235
DOI - 10.1002/cphc.201402444
Subject(s) - electron transfer , proton coupled electron transfer , proton , chemistry , chemical physics , photoinduced electron transfer , coherence (philosophical gambling strategy) , excitation , artificial photosynthesis , molecular physics , ab initio , coupling (piping) , photosynthetic reaction centre , molecular vibration , electron , atomic physics , molecule , physics , photochemistry , materials science , quantum mechanics , biochemistry , organic chemistry , photocatalysis , metallurgy , catalysis
Photoinduced electron transfer (ET) and proton‐coupled electron transfer (PCET) are fundamental processes in natural phenomena, most noticeably in photosynthesis. Time‐resolved spectroscopic evidence of coherent oscillatory behavior associated with these processes has been reported both in complex biological environments, as well as in biomimetic models for artificial photosynthesis. Here, we consider a few biomimetic models to investigate these processes in real‐time simulations based on ab initio molecular dynamics and Ehrenfest dynamics. This allows for a detailed analysis on how photon‐to‐charge conversion is promoted by a coupling of the electronic excitation with specific vibrational modes and with proton displacements. The ET process shows a characteristic coherence that is linked to the nuclear motion at the interface between donor and acceptor. We also show real‐time evidence of PCET in a benzimidazole–phenol redox relay.