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Title: Photoionization mass spectrometry of CH/sub 3/SH, CD/sub 3/SH, and CH/sub 3/SD: Heats of formation ofCH/sub 3/S/sup +/(CH/sub 2/SH/sup +/), CH/sub 2/S/sup +/, CH/sub 2/S, and HCS/sup +/

Abstract

Photoionization yield curves have been obtained for the major ions from CH/sub 3/SH. Auxiliary studies with selectively deuterated species reveal that CD/sub 3/S/sup +/ has a slightly lower threshold than CD/sub 2/SH/sup +/ from CD/sub 3/SH; but CH/sub 2/SD/sup +/ has a lower threshold than CH/sub 3/S/sup +/ from CH/sub 3/SD. An analysis of alternative interpretations is presented. The isotopic studies also imply that CH/sub 2/S/sup +/ is more stable than HCSH/sup +/, and HCS/sup +/ is more stable than CSH/sup +/. The value ..delta..H/sup 0//sub f/,0(HCS/sup +/)< or =259.2 +- 0.9 kcal/mol obtained in this study is in good agreement with a bracketed proton affinity for CS, but differs significantly from a recent ab initio calculation. This result confirms the view that HCS/sup +/ can be formed in interstellar clouds by exothermic reactions. The reaction CH/sub 3/S/sup +//CH/sub 2/SH/sup +/..-->..HCS/sup +/+H/sub 2/ proceeds weakly at threshold, and much more strongly after overcoming an activation barrier of approx.0.9 eV.

Authors:
; ; ;
Publication Date:
Research Org.:
Argonne National Laboratory, Argonne, Illinois 60439
OSTI Identifier:
6715951
DOE Contract Number:  
W-31-109-ENG-38
Resource Type:
Journal Article
Journal Name:
J. Chem. Phys.; (United States)
Additional Journal Information:
Journal Volume: 77:11
Country of Publication:
United States
Language:
English
Subject:
74 ATOMIC AND MOLECULAR PHYSICS; ORGANIC SULFUR COMPOUNDS; FORMATION HEAT; MASS SPECTROSCOPY; PHOTOIONIZATION; MOLECULAR IONS; THERMODYNAMIC PROPERTIES; CHARGED PARTICLES; ENTHALPY; IONIZATION; IONS; ORGANIC COMPOUNDS; PHYSICAL PROPERTIES; REACTION HEAT; SPECTROSCOPY; 640302* - Atomic, Molecular & Chemical Physics- Atomic & Molecular Properties & Theory

Citation Formats

Kutina, R E, Edwards, A K, Goodman, G L, and Berkowitz, J. Photoionization mass spectrometry of CH/sub 3/SH, CD/sub 3/SH, and CH/sub 3/SD: Heats of formation ofCH/sub 3/S/sup +/(CH/sub 2/SH/sup +/), CH/sub 2/S/sup +/, CH/sub 2/S, and HCS/sup +/. United States: N. p., 1982. Web.
Kutina, R E, Edwards, A K, Goodman, G L, & Berkowitz, J. Photoionization mass spectrometry of CH/sub 3/SH, CD/sub 3/SH, and CH/sub 3/SD: Heats of formation ofCH/sub 3/S/sup +/(CH/sub 2/SH/sup +/), CH/sub 2/S/sup +/, CH/sub 2/S, and HCS/sup +/. United States.
Kutina, R E, Edwards, A K, Goodman, G L, and Berkowitz, J. 1982. "Photoionization mass spectrometry of CH/sub 3/SH, CD/sub 3/SH, and CH/sub 3/SD: Heats of formation ofCH/sub 3/S/sup +/(CH/sub 2/SH/sup +/), CH/sub 2/S/sup +/, CH/sub 2/S, and HCS/sup +/". United States.
@article{osti_6715951,
title = {Photoionization mass spectrometry of CH/sub 3/SH, CD/sub 3/SH, and CH/sub 3/SD: Heats of formation ofCH/sub 3/S/sup +/(CH/sub 2/SH/sup +/), CH/sub 2/S/sup +/, CH/sub 2/S, and HCS/sup +/},
author = {Kutina, R E and Edwards, A K and Goodman, G L and Berkowitz, J},
abstractNote = {Photoionization yield curves have been obtained for the major ions from CH/sub 3/SH. Auxiliary studies with selectively deuterated species reveal that CD/sub 3/S/sup +/ has a slightly lower threshold than CD/sub 2/SH/sup +/ from CD/sub 3/SH; but CH/sub 2/SD/sup +/ has a lower threshold than CH/sub 3/S/sup +/ from CH/sub 3/SD. An analysis of alternative interpretations is presented. The isotopic studies also imply that CH/sub 2/S/sup +/ is more stable than HCSH/sup +/, and HCS/sup +/ is more stable than CSH/sup +/. The value ..delta..H/sup 0//sub f/,0(HCS/sup +/)< or =259.2 +- 0.9 kcal/mol obtained in this study is in good agreement with a bracketed proton affinity for CS, but differs significantly from a recent ab initio calculation. This result confirms the view that HCS/sup +/ can be formed in interstellar clouds by exothermic reactions. The reaction CH/sub 3/S/sup +//CH/sub 2/SH/sup +/..-->..HCS/sup +/+H/sub 2/ proceeds weakly at threshold, and much more strongly after overcoming an activation barrier of approx.0.9 eV.},
doi = {},
url = {https://www.osti.gov/biblio/6715951}, journal = {J. Chem. Phys.; (United States)},
number = ,
volume = 77:11,
place = {United States},
year = {Wed Dec 01 00:00:00 EST 1982},
month = {Wed Dec 01 00:00:00 EST 1982}
}