The radiative characteristics of hydrogen rovibronic states: II. The probabilities of the i 3Π g − , j 3Δ g − → b 3Σ u + , c 3Π u ± spontaneous transitions in H2, HD, and D2

Abstract

The absolute probabilities of radiative rovibronic transitions in the i 3Π − , j 3Δ − → c 3Π ± band systems of H2, HD, and D2 and the probabilities, integrated over wave numbers, of bound-free i 3Π − , i 3Π − , j 3Δ − → b 3Σ + transitions in H2 were calculated semiempirically. The experimental data were analyzed using the nonadiabatic model that included the electron-rotational interaction of the 3d 3Π g and 3d 3Δ g states in the pure precession approximation. The coefficients of the expansion of the wave functions of the rovibrational levels of radiative electronic states in Born-Oppenheimer basis functions were found from the experimental data on rovibronic terms. The dipole moments of the 3d 3Π g → 2p 3Σ + , 3d 3Π g → 2p 3Π u , and 3d 3Δ g → 2p 3Π u electronic transitions were determined from the measured relative probabilities of spontaneous transitions and radiative lifetimes of rovibronic levels by calculating vibronic matrix elements for ab initio potential curves. The semiempirical and ab initio data on the dipole moments and probabilities of spontaneous transitions are compared. The results obtained by comparing the transition probabilities between the corresponding triplet and singlet electronic states of H2 and D2 are presented.