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@ARTICLE{Sellner:136793,
author = {Sellner, Bernhard and Barbatti, Mario and Mueller, Thomas
and Domcke, Wolfgang and Lischka, Hans},
title = {{U}ltrafast non-adiabatic dynamics of ethylene including
{R}ydberg states},
journal = {Molecular physics},
volume = {111},
issn = {1362-3028},
address = {London},
publisher = {Taylor $\&$ Francis},
reportid = {FZJ-2013-03382},
pages = {1 - 12},
year = {2013},
note = {Online first},
abstract = {The photodynamics of ethylene has been studied by means of
ab initio surface-hopping dynamics using extended
multireference configuration interaction wavefunctions. At
the highest level, the explicit possibility of excited-state
CH dissociation and consideration of the Rydberg π−3s
state was included into the electronic wavefunction. The
initial dynamics is characterised by the torsional motion
and the crossing between the bright π−π * state with S
1, the latter having primarily Rydberg character with only a
minor contribution of the repulsive valence π−σ * state.
Due to back-rotation to planar structures after 17 fs, part
of the population flows into the Rydberg states. The
lifetime for this fraction of trajectories is significantly
longer than that for the valence population. An analysis of
the latter population shows that the decay to the ground
state proceeds mainly at the pyramidalised conical
intersection. Thus, no major qualitative mechanistic changes
as compared to previous dynamics simulations are observed
for the valence population. In the present work, a decay
time of 62 fs was found for the valence population.
Simulations performed for ethylene-d4 show a slowdown of the
torsional mode. However, since the crossing seam is reached
in a more direct way with less torsional oscillations, the
excited-state lifetime is almost unchanged as compared to
ethylene.},
cin = {JSC},
ddc = {530},
cid = {I:(DE-Juel1)JSC-20090406},
pnm = {411 - Computational Science and Mathematical Methods
(POF2-411)},
pid = {G:(DE-HGF)POF2-411},
typ = {PUB:(DE-HGF)16},
UT = {WOS:000327954200008},
doi = {10.1080/00268976.2013.813590},
url = {https://juser.fz-juelich.de/record/136793},
}