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Vibronic Coupling Effects in Spectroscopy and Non-adiabatic Transitions in Molecular Photodynamics

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Molecular Quantum Dynamics

Part of the book series: Physical Chemistry in Action ((PCIA))

Abstract

A brief historic and systematic survey is given of our efforts to elucidate important features of the nuclear motion on interacting potential energy surfaces (PESs). Starting with our early work in 1977, a variety of small to medium-sized polyatomic molecules have been treated by quantum-dynamical methods. As the key topological feature signalling the effects in question, conical intersections of PESs have been established. The associated strong nonadiabatic coupling effects manifest themselves as diffuse (at low resolution) or irregular (at high resolution) spectral structures upon electronic transitions. The concomitant fs electronic population decay governs the photophysical and photochemical properties of these systems. Representative examples with 2–5 strongly coupled electronic states are given, and the quantum nature of the phenomena is emphasized.

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Acknowledgements

The author is indebted to L.S. Cederbaum, W. Domcke and S. Mahapatra for a long-term collaboration on the vibronic coupling problem. It is also a pleasure to acknowledge a fruitful cooperation with E. Gromov, S. Kopec, C. Lévêque and A. Komainda on current problems in the field.

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  1. Theoretical Chemistry, Im Neuenheimer Feld 229, University of Heidelberg, 69120, Heidelberg, Germany

    Horst Köppel

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  1. Horst Köppel
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Correspondence to Horst Köppel .

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  1. Institut Charles GERHARDT - CNRS 5253, Université Montpellier 2, Montpellier Cedex, France

    Fabien Gatti

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Köppel, H. (2014). Vibronic Coupling Effects in Spectroscopy and Non-adiabatic Transitions in Molecular Photodynamics. In: Gatti, F. (eds) Molecular Quantum Dynamics. Physical Chemistry in Action. Springer, Berlin, Heidelberg. https://doi.org/10.1007/978-3-642-45290-1_6

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