Resonance-enhanced Multiphoton Ionisation Spectroscopy of Methanethiol

  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. Wales, N.P.L. 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: 1995

Volumen: 91

Número: 17

Páginas: 2715-2721

Tipo: Artículo

DOI: 10.1039/FT9959102715 SCOPUS: 2-s2.0-0007836346 GOOGLE SCHOLAR

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

Resumen

We report the first multiphoton study of excited electronic states of the methanethiol molecule. Members of four Rydberg series are identified via the two- and three-photon resonance enhancements they provide in the multiphoton ionisation spectrum of this molecule. Spectral analysis is aided by parallel measurements of the kinetic energies of the accompanying photoelectrons. Such studies also yield a refined value for the first ionisation limit of methanethiol: Ei = 76 260 ± 40 cm-1. Detailed inspection of the photoelectron spectra obtained following REMPI via all but the lowest energy resonances reveal the presence of 'slower' photoelectrons, the energies of which can be interpreted if we invoke near-resonant inter-Rydberg state vibronic mixing. It is suggested that such inter-Rydberg state vibronic mixing must be rather commonplace in polyatomic systems, especially in molecules like methanethiol where symmetry imposes few restrictions on the allowed state couplings.