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Nonadiabatic photodynamics and UV absorption spectrum of all-trans-octatetraene

The short-time molecular quantum dynamics of all-trans-octatetraene after electronic excitation to the first bright valence state is theoretically investigated. A semiempirical approach of a multireference configuration interaction based on density functional theory, the so called hybrid DFT/MRCI, i...

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Hauptverfasser: Lyskov, Igor (VerfasserIn) , Köppel, Horst (VerfasserIn) , Marian, Christel (VerfasserIn)
Dokumenttyp: Article (Journal)
Sprache:Englisch
Veröffentlicht: 2017
In: Physical chemistry, chemical physics
Year: 2017, Jahrgang: 19, Heft: 5, Pages: 3937-3947
ISSN:1463-9084
DOI:10.1039/C6CP07640H
Online-Zugang:Verlag, Volltext: http://dx.doi.org/10.1039/C6CP07640H
Verlag, Volltext: http://pubs.rsc.org/en/content/articlelanding/2017/cp/c6cp07640h
Volltext
Verfasserangaben:Igor Lyskov, Horst Köppel and Christel M. Marian
Beschreibung
Zusammenfassung:The short-time molecular quantum dynamics of all-trans-octatetraene after electronic excitation to the first bright valence state is theoretically investigated. A semiempirical approach of a multireference configuration interaction based on density functional theory, the so called hybrid DFT/MRCI, in both its original and redesigned formulations, is used for treating the electronic part of the problem. The nuclear kinetic part is defined with the help of symmetry-adapted internal coordinates also suitable for a large amplitude displacement. By incorporating ten in-plane and two out-of-plane nuclear degrees of freedom in the underlying Hamiltonian, the results of the time evolution of the excited wave packet are discussed. We show that the population transfer between the two coupled low-lying states in all-trans-octatetraene occurs in a 100-200 fs time regime. The calculated UV absorption spectra describe the main vibronic features correctly except for the band associated with the single-bond stretching motion which lacks intensity. The possible products of the photoisomerization in terms of symmetry-adapted coordinates are also discussed.
Beschreibung:First published on 06 Jan 2017
Gesehen am 29.06.2018
Beschreibung:Online Resource
ISSN:1463-9084
DOI:10.1039/C6CP07640H

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