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Related Experiment Videos

Rotationally Resolved Vacuum Ultraviolet Laser Spectra of the 37Cl2 11Sigma+u <-- X1Sigma+g Transition

Wang1, Okuda, Dimov

  • 1Department of Chemistry, University of Western Ontario, London, Ontario, N6A 5B7, Canada

Journal of Molecular Spectroscopy
|December 16, 1998
PubMed
Summary

This study presents new spectroscopic data for chlorine molecules (Cl2), revealing detailed insights into the electronic structure of the 1(1)Sigma+u state. These findings refine our understanding of molecular potentials and isotopic behavior.

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Area of Science:

  • Molecular Spectroscopy
  • Quantum Chemistry
  • Atomic and Molecular Physics

Background:

  • The electronic structure of Cl2 involves complex excited states, including the 1(1)Sigma+u state, influenced by Rydberg-ion-pair state interactions.
  • Previous studies have characterized the dominant transition, but detailed isotopic and rotational information for less abundant isotopes remained incomplete.

Purpose of the Study:

  • To obtain rotationally and isotopically resolved single-photon excitation spectra of jet-cooled Cl2.
  • To deduce rotational constants for various vibrational levels of the 37Cl2 isotopomer.
  • To test and refine analytical models of the 1(1)Sigma+u potential energy curve.

Main Methods:

  • Utilized tunable vacuum ultraviolet (VUV) laser generation via resonant four-wave difference mixing in Krypton gas.

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  • Employed (1 + 1 ) resonance-enhanced multiphoton ionization coupled with time-of-flight mass spectrometry for single isotopomer detection.
  • Recorded spectra in the 133–138 nm wavelength range.

    • Main Results:

    • Achieved rotationally and isotopically resolved spectra for Cl2.
    • Successfully deduced rotational constants for numerous vibrational levels (v ) of the 37Cl2 isotopomer.
    • Observed spectral features corresponding to both Rydberg-well-localized and ion-pair-delocalized states.

    Conclusions:

    • The experimental data provide crucial tests for analytical potential energy functions of the 1(1)Sigma+u state in Cl2.
    • The study enhances the understanding of molecular interactions and isotopic effects in excited electronic states.
    • This work refines theoretical models by providing precise experimental validation.