Perturbation of the radiative lifetimes of rovibronic levels of the nl complex of terms of a diatomic molecule

Abstract

Within the framework of a sufficiently general nonadiabatic model taking into account the interaction of an arbitrary finite number of electronic states and not requiring the smallness of a perturbation parameter, expressions have been obtained for the radiative lifetimes of the rovibronic levels of states of the nl complex of terms of a diatomic molecule. It is shown that the determination of ratios of the nonadiabatic and adiabatic radiative lifetimes for the rovibronic levels can be reduced to the solution of two independent problems (the determination of ratios of the adiabatic values of radiative lifetimes for the mutually perturbing states and determination of the expansion coefficients of the wave functions of rovibronic states in the Born-Oppenheimer basis set of wave functions) when the rovibronic states are perturbed by only a single rovibrational level of each electronic state or by an arbitrary number of rovibrational states of each electronic state provided that the potential curves of the combining states are similar and the dipole moments of electronic transitions weakly depend on the internuclear separation (which is quite a case for highly excited electronic states). To illustrate the efficiency of using the expressions obtained, the perturbations of the radiative lifetimes of rovibrational levels of the I1Πg− and J1Δ g−states of the 3d complex of terms of the H2 molecule were considered.