Effects of higher order Jahn-Teller coupling on the nuclear dynamics

In this paper effects of higher order Jahn-Teller coupling terms on the nonadiabatic dynamics are studied. Of particular interest is the case when the potential energy surfaces of the degenerate state show pronounced anharmonicity. In order to demonstrate the effects a two-dimensional Ecircle timese Jahn-Teller model system is treated which is based on the e' stretching vibration of the photoactive E-2' state of NO3 as a realistic example. The sixth order Ecircle timese Jahn-Teller Hamiltonian is derived in the diabatic representation which is valid for any system with a C-3 rotation axis. This diabatization scheme is compared to lower-order Jahn-Teller Hamiltonians and to symmetry adapted as well as ad hoc approximations. Lower-order potentials result in pronounced quantitative and qualitative differences in the dynamics, including differences in the evolution of mean values, the autocorrelation functions (and thus the corresponding spectra), and the electronic population evolution. In the particular example treated, the results of fourth and fifth order potentials are very similar to the sixth order reference system. In contrast, the approximate sixth order Hamiltonians, though the corresponding adiabatic surfaces seem to be nearly identical, results in pronounced differences. The possible consequences for the dynamics of realistic systems with higher dimensionality are briefly discussed. (C) 2004 American Institute of Physics.