Ab initio calculation of electronic transition moments for singlet excited states of the H 2 molecule

Abstract

Ab initio CI electronic dipole transition moments have been calculated for the transitions between singlet states of the hydrogen molecule correlating asymptotically with H( nl)+H(1 s) ( n=1,2,3). The investigated singlet–singlet transitions include the 30 ( n=3) inter-Rydberg transitions and the 32 transitions which may contribute to absorption in the far wings of the Balmer α line of atomic hydrogen perturbed by another hydrogen atom in its ground state. Results are presented for internuclear distances 1.0 a 0⩽ R⩽12 a 0. The present results compare well with the previous theoretical calculations available for about half of the transitions treated in the present work. Thirty eight new transitions are presented. Adiabatic potential energies for the 1 1 Δ u and 3 1 Π g and improved energies for the 3 1 Π u and 4 1 Π u states are reported as well.