Document Type



Final Published Version

Publication Title

The Journal of Chemical Physics



Publication Date

Winter 1-6-2016


Double-resonance laser spectroscopy via the E F 1Σg+, v'=6, J'=0-2 state was used to probe the high vibrational levels of the B"B-bar 1Σu+ state of molecular hydrogen. Resonantly-enhanced multiphoton ionization spectra were recorded by detecting ion production as a function of energy using a time of flight mass spectrometer. New measurements of energies for the v=51-66 levels for the B"B-bar state of H2 are reported, which, taken with previous results, span the v=46-69 vibrational levels. Results for energy levels are compared to theoretical close-coupled calculations [L. Wolniewicz, T. Orlikowski, and G. Staszewska, J. Mol. Spec. 238, 118 (2006)]. The average difference between the 84 measured energies and calculated energies is -3.8 cm-1 with a standard deviation of 5.3 cm-1. This level of agreement showcases the success of the theoretical calculations in accounting for the strong rovibronic mixing of the 1Σu+ and 1Πu+ states. Due to the ion-pair character of the outer well, the observed energies of the vibrational levels below the third dissociation limit smoothly connect with previously observed energies of ion-pair states above this limit. The results provide an opportunity for testing a heavy Rydberg multi-channel quantum defect analysis of the high vibrational states below the third dissociation limit.