Beyond Born-Oppenheimer treatment on spectroscopic and scattering processes

Abstract

We review the formulation of beyond Born-Oppenheimer (BBO) theory based on first principle for the construction of diabatic potential energy surfaces (PESs) both for few important spectroscopic systems, viz., Na 3 cluster, NO 2 radical as well as scattering process like D + + H 2 . The essential theoretical development leading to the BBO equations are thoroughly discussed. It has been found that the above molecular systems posses numerous nonadiabatic interactions that range from Jahn-Teller, Renner-Teller types of conical intersections along with strong pseudo Jahn-Teller couplings between various electronic states. We have calculated the adiabatic PESs and nonadiabatic coupling terms for those systems and subsequently performed adiabatic-to-diabatic transformation to construct smooth, symmetric and continuous diabatic potential energy matrix. Nuclear dynamics has been performed on the diabatic PESs of Na 3 and NO 2 to simulate the photoelectron spectra that match quite well with the experimentally measured ones. Moreover, we have carried out reactive scattering dynamics on the adiabatic and diabatic surfaces of system to reproduce experimental cross sections for reactive charge and non-charge transfer processes.