A new canonical perturbation procedure for studying nonadiabatic dynamics - Archive ouverte HAL Accéder directement au contenu
Article Dans Une Revue Chemical Physics Letters Année : 2001

A new canonical perturbation procedure for studying nonadiabatic dynamics

Résumé

We propose a new canonical perturbation procedure, based on Van Vleck's theory, for investigating nonadiabatic (i.e., non Born–Oppenheimer) dynamics. The basic idea is to let the unitary transformations depend on the matrix representations of angular momentum operators. The new procedure is applied to a simple model with two 2-dimensional diabatic electronic surfaces coupled by a λq term, which to some extent mimicks the bending and antisymmetric stretching degrees of freedom of NO2 in the ground and first excited electronic states. It is shown that the anharmonicities induced in the lowest surface by the coupling to the excited one are very precisely obtained from the proposed procedure.

Dates et versions

hal-00508459 , version 1 (03-08-2010)

Identifiants

Citer

Dominique Sugny, Marc Joyeux. A new canonical perturbation procedure for studying nonadiabatic dynamics. Chemical Physics Letters, 2001, 337 (4-6), pp.319-326. ⟨10.1016/S0009-2614(01)00206-8⟩. ⟨hal-00508459⟩
124 Consultations
0 Téléchargements

Altmetric

Partager

Gmail Facebook X LinkedIn More