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Title: Vibrational autoionization of state-selective jet-cooled methanethiol (CH 3SH) investigated with infrared + vacuum-ultraviolet photoionization

Vibrational autoionization of Rydberg states provides key information about nonadiabatic processes above an ionization threshold. In this work, we employed time-of-flight mass detection of CH 3SH + to record vibrational-state selective photo-ionization efficiency (PIE) spectra of jet-cooled methanethiol (CH 3SH) on exciting CH 3SH to a specific vibrationally excited state with an infrared (IR) laser, followed by excitation with a tunable laser in the vacuum-ultraviolet (VUV) region for ionization. Autoionizing Rydberg states assigned to the ns, np, nd and nf series are identified. When IR light at 2601 (ν 3, SH stretching mode) and 2948 cm -12, CH 3 symmetric stretching mode) was employed, the Rydberg series converged to the respective vibrationally excited (ν 3 and ν 2) states of CH 3SH +. When IR light at 3014 cm -1 (overlapped ν 19, CH 3 antisymmetric stretching and CH 2 antisymmetric stretching modes) was employed, Rydberg series converging to two vibrationally excited states (ν 1 and ν 9) of CH 3SH + were observed. When IR light at 2867 cm -1 (2ν 10, overtone of CH 3 deformation mode) and 2892 cm -1 (2ν 4, overtone of CH 2 scissoring mode) was employed, both Δν = -1more » and Δν = -2 ionization transitions were observed; there is evidence for direct ionization from the initial state into the CH 3SH +4 + = 1) continuum. In all observed IR-VUV-PIE spectra, the ns and nd series show intensity greater than the other Rydberg series, which is consistent with the fact that the highest-occupied molecular orbital of CH 3SH is a p-like lone pair orbital on the S atom. Finally, the quantum yields for autoionization of various vibrational excited states are discussed. Values of ν 1 = 3035, ν 2 = 2884, ν 3 = 2514, and ν 9 = 2936 cm -1 for CH 3SH + derived from the converged limits agree satisfactorily with values observed for Ar-tagged CH 3SH + at 3026, 2879, 2502, and 2933 cm -1.« less
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  1. National Chiao Tung University, Hsinchu (Taiwan). Department of Applied Chemistry and Institute of Molecular Science
  2. Argonne National Lab. (ANL), Argonne, IL (United States)
  3. National Chiao Tung University, Hsinchu (Taiwan). Department of Applied Chemistry and Institute of Molecular Science; Institute of Atomic and Molecular Sciences, Academia Sinica, Taipei (Taiwan)
Publication Date:
Grant/Contract Number:
Accepted Manuscript
Journal Name:
Physical Chemistry Chemical Physics. PCCP (Print)
Additional Journal Information:
Journal Name: Physical Chemistry Chemical Physics. PCCP (Print); Journal Volume: 19; Journal Issue: 43; Journal ID: ISSN 1463-9076
Royal Society of Chemistry
Research Org:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division
Country of Publication:
United States
OSTI Identifier: