Experimental and theoretical investigations of the He⋯I2 rovibronic spectra in the I2 B-X, 20-0 region

Sara E. Ray, Anne B. McCoy, John J. Glennon, Joshua P. Darr, Elizabeth J. Fesser, Jeffrey R. Lancaster, Richard A. Loomis

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Abstract

The laser-induced fluorescence and action spectra of I2 in a helium supersonic expansion have been recorded in the I2 B-X, 20-0 region. Two features are identified within the spectra. The lower-energy feature arises from transitions between states that are localized in a T-shaped conformation on both the X - and B -state potentials. The higher-energy feature reflects transitions from states that are localized in a linear conformation on the X state to states that have energies that are larger than the barrier for free rotation of the rare gas atom about the I2 molecule on the B -state potential. Ground-state binding energies of 16.6(6) and 16.3 (6) cm-1 were determined for the T-shaped and linear conformers, respectively. These spectra are compared to those calculated using the experimentally determined rotational temperatures. Based on the agreement between the experimental and calculated spectra, the binding energies of the J′ =0 states with 0 and 2-6 quanta of excitation in the He I2 bending mode on the B state were determined. Several models for the B -state potential were used to investigate the origins of the shape of the contour of the higher-energy feature in the spectra for He I2 and He Br2. The shape of the contours was found to be relatively insensitive to the choice of potential. This leads us to believe that the spectra of these systems are relatively insensitive to the parameters of the B -state potential energy surface and are more sensitive to properties of the halogen molecule.

Original languageEnglish (US)
Article number164314
JournalJournal of Chemical Physics
Volume125
Issue number16
DOIs
StatePublished - Nov 6 2006

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ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

Cite this

Ray, S. E., McCoy, A. B., Glennon, J. J., Darr, J. P., Fesser, E. J., Lancaster, J. R., & Loomis, R. A. (2006). Experimental and theoretical investigations of the He⋯I2 rovibronic spectra in the I2 B-X, 20-0 region. Journal of Chemical Physics, 125(16), [164314]. https://doi.org/10.1063/1.2363378