Unified semiclassical theory for the two-state system: An analytical solution for general nonadiabatic tunneling

ChaoYuan Zhu*, Sheng Hsien Lin

*Corresponding author for this work

Research output: Contribution to journalArticle

11 Scopus citations

Abstract

Unified semiclasical solution for general nonadiabatic tunneling between two adiabatic potential energy surfaces is established by employing unified semiclassical solution for pure nonadiabatic transition [C. Zhu, J. Chem. Phys. 105, 4159 (1996)] with the certain symmetry transformation. This symmetry comes from a detailed analysis of the reduced scattering matrix for Landau-Zener type of crossing as a special case of nonadiabatic transition and nonadiabatic tunneling. Traditional classification of crossing and noncrossing types of nonadiabatic transition can be quantitatively defined by the rotation angle of adiabatic-to-diabatic transformation, and this rotational angle enters the analytical solution for general nonadiabatic tunneling. The certain two-state exponential potential models are employed for numerical tests, and the calculations from the present general nonadiabatic tunneling formula are demonstrated in very good agreement with the results from exact quantum mechanical calculations. The present general nonadiabatic tunneling formula can be incorporated with various mixed quantum-classical methods for modeling electronically nonadiabatic processes in photochemistry.

Original languageEnglish
Article number044104
JournalJournal of Chemical Physics
Volume125
Issue number4
DOIs
StatePublished - 11 Aug 2006

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