TY  - JOUR
AU  - Uspenskiy, Igor
AU  - Strodel, Birgit
AU  - Stock, Gerhard
TI  - Classical calculation of transient absorption spectra monitoring ultrafast electron transfer processes
JO  - Journal of chemical theory and computation
VL  - 2
IS  - 6
SN  - 1549-9626
CY  - Washington, DC
M1  - FZJ-2018-07141
SP  - 1605 - 1617
PY  - 2006
AB  - 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.
LB  - PUB:(DE-HGF)16
C6  - pmid:26627031
UR  - <Go to ISI:>//WOS:000241992200015
DO  - DOI:10.1021/ct6002127
UR  - https://juser.fz-juelich.de/record/858241
ER  -