New ab initio Potential Energy Curve and Vibrational Levels for the B1Σu+ State of the Hydrogen Molecule

Abstract

The Born–Oppenheimer potential energy curve for the B1Σu+ state of the hydrogen molecule has been computed using a wave-function in the form of an 88 term expansion in elliptic coordinates and including the interelectronic distance. At R = Re the computed energy is 5.2 cm−1 lower than the previous most accurate value, in agreement with the prediction by Dabrowski and Herzberg. The new potential energy curve, with the previously computed adiabatic corrections, has been used to calculate the vibrational levels for H2, HD, and D2. The resulting dissociation energies differ from the experimental values by less than 1 cm−1. The discrepancies between the theoretical and experimental energies for various vibrational levels amount up to 12 cm−1 for H2 and 8 cm−1 for D2. Their analysis suggests that most of the discrepancy is due to the nonadiabatic effects, but partly also to incomplete convergence of the Born–Oppenheimer potential energy curve, especially at large internuclear separations.