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@ARTICLE{Ruckenbauer:15678,
author = {Ruckenbauer, M. and Barbatti, M. and Sellner, B. and
Müller, Th. and Lischka, H.},
title = {{A}zomethane: {N}onadiabatic {P}hotodynamical {S}imulations
in {S}olution},
journal = {The journal of physical chemistry / A},
volume = {114},
issn = {1089-5639},
address = {Washington, DC},
publisher = {Soc.},
reportid = {PreJuSER-15678},
pages = {12585 - 12590},
year = {2010},
note = {This work was supported by the Austrian Science Fund within
the framework of the Special Research Programs F16 (Advanced
Light Sources) and F41 (ViCoM) and Project P18411-N19. The
authors are also thankful for the technical support and
computer time at the VSC-Vienna Scientific Cluster (Project
nos. 70019 and 70151) and at the Luna-Cluster of the
Department of Scientific Computing, University of Vienna.
Displays of molecular structures were made with VMD. VMD was
developed with NTH support by the Theoretical and
Computational Biophysics group at the Beckman Institute,
University of Illinois at Urbana-Champaign
(http://www.ks.uiuc.edu/Research/vmd/).},
abstract = {The nonadiabatic deactivation of trans-azomethane starting
from the nπ* state has been investigated in gas phase,
water, and n-hexane using an on-the-fly surface-hopping
method. A quantum mechanical/molecular mechanics (QM/MM)
approach was used employing a flexible quantum chemical
level for the description of electronically excited states
and bond dissociation (generalized valence bond
perfect-pairing complete active space). The solvent effect
on the lifetime and structural parameters of azomethane was
investigated in detail. The calculations show that the
nonadiabatic deactivation is characterized by a CNNC
torsion, mainly impeded by mechanic interaction with the
solvent molecules. The similar characteristics of the
dynamics in polar and nonpolar solvent indicate that solvent
effects based on electrostatic interactions do not play a
major role. Lifetimes increase by about 20 fs for both
solvents with respect to the 113 fs found for the gas phase.
The present subpicosecond dynamics also nicely show an
example of the suppression of C-N dissociation by the
solvent cage.},
keywords = {Azo Compounds: chemistry / Hexanes: chemistry / Models,
Molecular / Photochemistry / Quantum Theory / Solutions /
Solvents: chemistry / Water: chemistry / Azo Compounds (NLM
Chemicals) / Hexanes (NLM Chemicals) / Solutions (NLM
Chemicals) / Solvents (NLM Chemicals) / n-hexane (NLM
Chemicals) / azomethane (NLM Chemicals) / Water (NLM
Chemicals) / J (WoSType)},
cin = {JSC},
ddc = {530},
cid = {I:(DE-Juel1)JSC-20090406},
pnm = {Scientific Computing (FUEK411) / 411 - Computational
Science and Mathematical Methods (POF2-411)},
pid = {G:(DE-Juel1)FUEK411 / G:(DE-HGF)POF2-411},
shelfmark = {Chemistry, Physical / Physics, Atomic, Molecular $\&$
Chemical},
typ = {PUB:(DE-HGF)16},
pubmed = {pmid:21070061},
UT = {WOS:000284738500004},
doi = {10.1021/jp108844g},
url = {https://juser.fz-juelich.de/record/15678},
}