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Quantum-classical modeling of photoisomerization of polyatomic molecules

Journal Article · · Journal of Chemical Physics
DOI:https://doi.org/10.1063/1.3368644· OSTI ID:21559849
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  1. Abteilung Spektroskopie und Photochemische Kinetik, Max-Planck-Institut fuer Biophysikalische Chemie, Am Fassberg, D-37077 Goettingen (Germany)
A new method, non-Markovian quantum-classical approximation (NQCA), is suggested to model the photoisomerization of polyatomic molecules. The NQCA method can be successfully applied to follow the photoisomerization process for a wide class of reacting systems, namely, those for which the time scale required for the equilibration in the phase space of the potential energy surface (PESs) is short compared to the time scale of the transitions between them. Such a situation is quite typical for the nonadiabatic transitions between the different electronic states in polyatomic molecules, where a high density of vibronic states facilitates the intramolecular vibrational energy redistribution, thus providing an efficient relaxation for the phase space distribution. The NQCA can easily be combined with molecular dynamics and quantum-chemical methods to describe the evolution of the classical degrees of freedom and the quantum part of the problem.
OSTI ID:
21559849
Journal Information:
Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 13 Vol. 132; ISSN JCPSA6; ISSN 0021-9606
Country of Publication:
United States
Language:
English