標題: Unified semiclassical theory for the two-state system: An analytical solution for general nonadiabatic tunneling
作者: Zhu, Chaoyuan
Lin, Sheng Hsien
應用化學系
應用化學系分子科學碩博班
Department of Applied Chemistry
Institute of Molecular science
公開日期: 28-Jul-2006
摘要: 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. (c) 2006 American Institute of Physics.
URI: http://dx.doi.org/10.1063/1.2227399
http://hdl.handle.net/11536/12006
ISSN: 0021-9606
DOI: 10.1063/1.2227399
期刊: JOURNAL OF CHEMICAL PHYSICS
Volume: 125
Issue: 4
結束頁: 
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