Referenced in: none

Automatically associated channels: Kir2.3

Title: Observations of the high vibrational levels of the B('')B̄ (1)Σu (+) state of H2.

Authors: A M Chartrand, W Duan, R C Ekey, E F McCormack

Journal, date & volume: J Chem Phys, 2016 Jan 7 , 144, 014307

PubMed link: http://www.ncbi.nlm.nih.gov/pubmed/26747806

Abstract
Double-resonance laser spectroscopy via the EF (1)Σg (+),v(')=6,J(')=0-2 state was used to probe the high vibrational levels of the B('')B̄ (1)Σu (+) 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('')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 (1)Σu (+) and (1)Πu (+) 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.