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Vibrational autoionization of Rydberg states provides key information about nonadiabatic processes above an ionization threshold. We employed time-of-flight mass detection of CH 3 SH + o record vibrational-state selective photo-ionization efficiency (PIE) spectra of jet-cooled methanethiol (CH 3 SH) on exciting CH 3 SH 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 -1 (ν 2 , CH 3 symmetric stretching mode) was employed, the Rydberg series converged to the respective vibrationally excited (ν 3 and ν 2 ) states of CH 3 SH + . When IR light at 3014 cm -1 (overlapped ν 1 /ν 9 , 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 3 SH + 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 = -1 and Δν = -2 ionization transitions were observed; there is evidence for direct ionization from the initial state into the CH 3 SH + (ν 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 3 SH is a p-like lone pair orbital on the S atom. 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 3 SH + derived from the converged limits agree satisfactorily with values observed for Ar-tagged CH 3 SH + at 3026, 2879, 2502, and 2933 cm -1 .

physical chemistry chemical physics

Vibrational autoionization of state-selective jet-cooled methanethiol (CH<sub>3</sub>SH) investigated with infrared + vacuum-ultraviolet photoionization

Vibrational autoionization of state-selective jet-cooled methanethiol (CH3SH) investigated with infrared + vacuum-ultraviolet photoionization

Vibrational autoionization of state-selective jet-cooled methanethiol (CH₃SH) investigated with infrared + vacuum-ultraviolet photoionization