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

Vibrational autoionization of Rydberg states provides key information about nonadiabatic processes above an ionization threshold. We employed time-of-flight mass detection of CH₃SH⁺ to record vibrational-state selective photo-ionization efficiency (PIE) spectra of jet-cooled methanethiol (CH₃SH) on exciting CH₃SH 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 (ν₃, SH stretching mode) and 2948 cm^-1 (ν₂, CH₃ symmetric stretching mode) was employed, the Rydberg series converged to the respective vibrationally excited (ν₃ and ν₂) states of CH₃SH⁺. When IR light at 3014 cm^-1 (overlapped ν₁/ν₉, CH₃ antisymmetric stretching and CH₂ antisymmetric stretching modes) was employed, Rydberg series converging to two vibrationally excited states (ν₁ and ν₉) of CH₃SH⁺ were observed. When IR light at 2867 cm^-1 (2ν₁₀, overtone of CH₃ deformation mode) and 2892 cm^-1 (2ν₄, overtone of CH₂ 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 CH₃SH⁺ (ν₄⁺ = 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 CH₃SH 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 ν₁ = 3035, ν₂ = 2884, ν₃ = 2514, and ν₉ = 2936 cm^-1 for CH₃SH⁺ derived from the converged limits agree satisfactorily with values observed for Ar-tagged CH₃SH⁺ at 3026, 2879, 2502, and 2933 cm^-1.