The radiative characteristics of the rovibronic states of the hydrogen molecule: III. The probabilities of the h 3Σ g + , g 3Σ g + , i 3Π g + , j 3Δ g + → c 3Π u ± spontaneous transitions in the H2 molecule

Abstract

The absolute values of radiative transition probabilities were obtained semiempirically for the h3Σg+, g3Σg+, i3Πg+, j3Δg+ → c3Πu± band systems of the H2 molecule. The experimental data on rovibronic terms were analyzed using the nonadiabatic model taking into account the interaction of the 3s3Σg+, 3d3Σg+, 3d3Πg, and 3d3Δg states in the pure precession approximation. Published semiempirical values of the expansion coefficients of the perturbed wave functions of the rovibronic levels of upper electronic states over the Born-Oppenheimer basis set were used. The dipole moments of the 3s3Σg+, 3d3Σg+, 3d3Πg, and 3d3Δg → 2p3Πu electronic transitions were found from the measured relative probabilities of spontaneous transitions and radiative lifetimes of rovibronic levels with the use of the calculated overlap integrals between the vibrational wave functions of the combining states obtained from ab initio potential curves. The probabilities of transitions from the rovibronic levels of the 3d3Λg− and 3d3Λg+ states were found to be substantially different (by factors of up to 20 and 3.5 for transitions from the i3Πg and j3Δg states, respectively) because of qualitatively different nonadiabatic effects of the perturbation of electronic states with different Kronig symmetries (Λ+ and Λ−).