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

Physical Chemistry Chemical Physics : PCCP
Min XieYuan-Pern Lee

Abstract

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 f...Continue Reading

References

Sep 16, 2000·Physical Review Letters·C A Raptis, S T Pratt
Jan 1, 1997·Annual Review of Physical Chemistry·F Merkt
Mar 31, 2005·Annual Review of Physical Chemistry·S T Pratt
Jun 7, 2014·Pharmacological Reports : PR·Ana MijuškovićDuško Blagojević
Jan 17, 2015·The Journal of Chemical Physics·Weizhan XiaoLiusi Sheng
Sep 8, 2016·Physical Chemistry Chemical Physics : PCCP·R L Hudson

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Citations

Aug 26, 2020·Physical Chemistry Chemical Physics : PCCP·Heesung Lee, Sang Kyu Kim

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Methods Mentioned

BETA
photodepletion

Software Mentioned

REMPI
Gaussian
ezSpectrum

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