Higher order (A+E) multiply sign in circle e pseudo-Jahn-Teller coupling.
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 C(3) main rotational axis. The PJT coupling terms up to sixth order are derived by symmetry considerations for this general (A+E) multiply sign in circle e case. The obtained expression for the 3 x 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 D(3h), C(3v), C(3h), and C(3), is discussed. The effect of the higher order PJT coupling is tested by a two-dimensional model study based on the e 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.
Eisfeld
Wolfgang
W
Lehrstuhl für Theoretische Chemie, Department Chemie, Technische Universität München, D-85747 Garching, Germany. wolfgang.eisfeld@ch.tum.de
Viel
Alexandra
A