Vibrational autoionization of state-selective jet-cooled methanethiol (CH3SH) investigated with infrared + vacuum-ultraviolet photoionization
Abstract
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 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 allmore »
- Authors:
-
- National Chiao Tung University, Hsinchu (Taiwan). Department of Applied Chemistry and Institute of Molecular Science
- Argonne National Lab. (ANL), Argonne, IL (United States)
- 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:
- Research Org.:
- Argonne National Laboratory (ANL), Argonne, IL (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division
- OSTI Identifier:
- 1420066
- Grant/Contract Number:
- AC02-06CH11357
- Resource Type:
- 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
- Publisher:
- Royal Society of Chemistry
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Xie, Min, Shen, Zhitao, Pratt, S. T., and Lee, Yuan-Pern. Vibrational autoionization of state-selective jet-cooled methanethiol (CH3SH) investigated with infrared + vacuum-ultraviolet photoionization. United States: N. p., 2017.
Web. doi:10.1039/C7CP06433K.
Xie, Min, Shen, Zhitao, Pratt, S. T., & Lee, Yuan-Pern. Vibrational autoionization of state-selective jet-cooled methanethiol (CH3SH) investigated with infrared + vacuum-ultraviolet photoionization. United States. https://doi.org/10.1039/C7CP06433K
Xie, Min, Shen, Zhitao, Pratt, S. T., and Lee, Yuan-Pern. Tue .
"Vibrational autoionization of state-selective jet-cooled methanethiol (CH3SH) investigated with infrared + vacuum-ultraviolet photoionization". United States. https://doi.org/10.1039/C7CP06433K. https://www.osti.gov/servlets/purl/1420066.
@article{osti_1420066,
title = {Vibrational autoionization of state-selective jet-cooled methanethiol (CH3SH) investigated with infrared + vacuum-ultraviolet photoionization},
author = {Xie, Min and Shen, Zhitao and Pratt, S. T. and Lee, Yuan-Pern},
abstractNote = {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 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. Finally, 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.},
doi = {10.1039/C7CP06433K},
journal = {Physical Chemistry Chemical Physics. PCCP (Print)},
number = 43,
volume = 19,
place = {United States},
year = {Tue Oct 24 00:00:00 EDT 2017},
month = {Tue Oct 24 00:00:00 EDT 2017}
}
Web of Science
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