The Journal of Chemical Physics, Vol. 144, Issue 014307, January 2016. Co-written with A. M. Chartrand, W. Duan, and R. C. Ekey.
Double-resonance laser spectroscopy via the E F, v' = 6, J' = 0–2 state was used to probe the high vibrational levels of the B′′B̄ state of molecular hydrogen. Resonantly enhanced multiphotonionization 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′′B̄ 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. Spectrosc. 238, 118–126 (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 Σ and Π 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.