Premium
Excitation Frequency Dependence of Ultrafast Photoinduced Charge Transfer Dynamics
Author(s) -
Nazarov Alexey E.,
Ivanov Anatoly I.
Publication year - 2017
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/kin.21129
Subject(s) - chemistry , excitation , ultrashort pulse , charge (physics) , dynamics (music) , chemical physics , transfer (computing) , atomic physics , optics , physics , quantum mechanics , laser , parallel computing , computer science , acoustics
The dependence of the photoinduced charge transfer rate constant on the pump pulse carrier frequency is shown to be strong, and it is considerably affected by the value of the reorganization energy of low‐frequency modes at the stage of excitation. In the area of small values of the reorganization energy, the dependence of the charge transfer rate constant on the pump pulse carrier frequency is strongly nonmonotonic that is caused by vibrational resonances and variation of the initial position of the wave packet on the term of the locally excited state. Increasing the reorganization energy smoothes the dependence. The smoothing is caused by the broadening of the vibrational resonances and their overlapping. The high‐frequency vibrational mode excitation typically accelerates the charge transfer in both areas of high and low exergonicity and decelerates it in the vicinity of the Marcus barrierless region.