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Article Dans Une Revue Journal of Chemical Physics Année : 2005

Higher order (A+E)⊗e pseudo-Jahn–Teller coupling

Résumé

The pseudo-Jahn–Teller (PJT) coupling of a nondegenerate state A with a twofold degenerate state E by a degenerate vibrational mode e is studied for a general system with a C3 main rotational axis. The PJT coupling terms up to sixth order are derived by symmetry considerations for this general (A+E)⊗e case. The obtained expression for the 3×3 diabatic potential energy matrix is found to be closely related to the expression recently developed for the higher order Jahn–Teller case [A. Viel and W. Eisfeld, J. Chem. Phys. 120, 4603 (2004)]. The dynamical PJT coupling, which can arise for states of appropriate symmetry if one of the vibrational modes induces a change of the nuclear point group between D3h, C3v, C3h, and C3, is discussed. The effect of the higher order PJT coupling is tested by a two-dimensional model study based on the ee bending mode of NH+3. The models are analyzed by fitting the two-dimensional potential energy surfaces. The significance of the higher order terms on the nonadiabatic dynamics is demonstrated by quantum wave packet propagations.
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Dates et versions

hal-01118370 , version 1 (10-07-2017)

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Wolfgang Eisfeld, Alexandra Viel. Higher order (A+E)⊗e pseudo-Jahn–Teller coupling. Journal of Chemical Physics, 2005, 122 (20), pp.204317. ⟨10.1063/1.1904594⟩. ⟨hal-01118370⟩
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