The ƒ3Σ+u State of the Hydrogen Molecule

• Published in: Journal of molecular spectroscopy 1994-07, Vol.166 (1), p.12-19
• Main Authors: Kolos, W., Rychlewski, J.
• Format: Article
• Language: English
• Subjects: Atomic and molecular physics; Exact sciences and technology; Molecular properties and interactions with photons; Physics; Properties of molecules and molecular ions; Rotation, vibration and vibration-rotation constants; Vibration-rotation analysis
• ISSN: 0022-2852; 1096-083X
• DOI: 10.1006/jmsp.1994.1167

The Born-Oppenheimer potential energy curve and the adiabatic corrections for the ƒ3Σ+u state of the hydrogen molecule have been calculated using explicitly correlated wavefunctions in elliptic coordinates. The calculated potential energy curve is more accurate than any previous results for this state. The energies of the vibrational levels and rotational constants for the ƒ3Σ+u state also have been computed. It is shown that the discrepancy between theoretical and experimental term values for H2 and D2 cannot be attributed to any known effect. The above discrepancies in Tv for D2 are caused presumably by a heterogeneous nonadiabatic effect. In conclusion we suggest that for H2 the experimental term values for v = 0 should be revised.