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@ARTICLE{Uspenskiy:858241,
author = {Uspenskiy, Igor and Strodel, Birgit and Stock, Gerhard},
title = {{C}lassical calculation of transient absorption spectra
monitoring ultrafast electron transfer processes},
journal = {Journal of chemical theory and computation},
volume = {2},
number = {6},
issn = {1549-9626},
address = {Washington, DC},
reportid = {FZJ-2018-07141},
pages = {1605 - 1617},
year = {2006},
abstract = {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.},
cin = {ICS-6},
ddc = {610},
cid = {I:(DE-Juel1)ICS-6-20110106},
pnm = {551 - Functional Macromolecules and Complexes (POF3-551)},
pid = {G:(DE-HGF)POF3-551},
typ = {PUB:(DE-HGF)16},
pubmed = {pmid:26627031},
UT = {WOS:000241992200015},
doi = {10.1021/ct6002127},
url = {https://juser.fz-juelich.de/record/858241},
}