%0 Journal Article
%A Uspenskiy, Igor
%A Strodel, Birgit
%A Stock, Gerhard
%T Classical calculation of transient absorption spectra monitoring ultrafast electron transfer processes
%J Journal of chemical theory and computation
%V 2
%N 6
%@ 1549-9626
%C Washington, DC
%M FZJ-2018-07141
%P 1605 - 1617
%D 2006
%X Classical formulations are considered that allow for the calculation of time- and frequency-resolved pump−probe spectra of nonadiabatically coupled molecular systems. When the semiclassical Franck−Condon approximation in the theoretical framework of the doorway-window formalism is employed, various first- and second-order expressions for the classical doorway and window functions are derived. Moreover, a classical analogue of the electronic dipole transition operator is employed. When established models describing ultrafast photoinduced electron transfer are adopted, it is found that the first-order approximations give rise to spurious structures of the time-resolved signal, which indicate that these approximations fail to correctly account for the averaging effect caused by finite pulses. The higher-order approximations, on the other hand, are shown to give a fairly accurate description of the transient absorption spectrum. By comparing to exact quantum-mechanical calculations, the merits and shortcomings of the various approaches as well as the generally achievable accuracy of a classical modeling of optical spectra is discussed.
%F PUB:(DE-HGF)16
%9 Journal Article
%$ pmid:26627031
%U <Go to ISI:>//WOS:000241992200015
%R 10.1021/ct6002127
%U https://juser.fz-juelich.de/record/858241