Resonance-enhanced Multiphoton Ionisation Spectroscopy of Thiirane

  1. Morgan, R.A. 3
  2. Puyuelo, P. 13
  3. Howe, J.D. 3
  4. Ashfold, M.N.R. 3
  5. Buma, W.J. 2
  6. Milan, J.B. 2
  7. De Lange, C.A. 2
  1. 1 Universidad de La Rioja
    info

    Universidad de La Rioja

    Logroño, España

    ROR https://ror.org/0553yr311

  2. 2 University of Amsterdam
    info

    University of Amsterdam

    Ámsterdam, Holanda

    ROR https://ror.org/04dkp9463

  3. 3 University of Bristol
    info

    University of Bristol

    Brístol, Reino Unido

    ROR https://ror.org/0524sp257

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Revista:
Journal of the Chemical Society. Faraday transactions Print

ISSN: 0956-5000

Año de publicación: 1994

Volumen: 90

Número: 24

Páginas: 3591-3599

Tipo: Artículo

DOI: 10.1039/FT9949003591 SCOPUS: 2-s2.0-0000407004 GOOGLE SCHOLAR

Otras publicaciones en: Journal of the Chemical Society. Faraday transactions Print

Resumen

We present a new and more extensive interpretation of the vertical electronic spectrum of the thiirane molecule based on (i) analysis of observed two- and three-photon resonance enhancements in the wavelength-resolved multiphoton ionisation spectrum of jet-cooled thiirane and (ii) measurements of the kinetic energies of the photoelectrons accompanying the multiphoton ionisation process. Six Rydberg series are identified, including the four series identified in previous one-photon vacuum ultraviolet absorption studies of this molecule. Series assignments are offered based on the measured quantum defects, their relative two- and three-photon transition strengths and the dependence (if any) of the two-photon transition intensities upon changing from linearly to circularly polarised photoexcitation. Our analysis suggests that, as in H 2S, many of the Rydberg orbitals have hybrid/character; it also points to the need for some revision of all previous interpretations of the electronic spectrum of the thiirane molecule.