Observations of the high vibrational levels of the B′′B̄ 1Σ+u state of H2

Authors

A. M. Chartrand
W. Duan
R. C. Ekey
Elizabeth McCormack, emccorma@brynmawr.eduFollow

Document Type

Article

Version

Final Published Version

Publication Title

The Journal of Chemical Physics

Volume

144

Publication Date

2016

Abstract

Double-resonance laser spectroscopy via the E F ¹Σ⁺_g, v' = 6, J' = 0–2 state was used to probe the high vibrational levels of the B′′B̄ ¹Σ⁺_u 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 B00B ̄ 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 ¹Σ_u⁺ and ¹Π_u⁺ 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.

Publisher's Statement

© 2016 American Institute of Physics

Citation

A. M. Chartrand, W. Duan, R. C. Ekey, and E. F. McCormack. "Observations of the high vibrational levels of the B′′B̄ 1Σ+u state of H2," The Journal of Chemical Physics 144, 014307 (2016).

DOI

http://dx.doi.org/10.1063/1.4939079