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Title: Experimental and theoretical studies of the reactions of ground-state sulfur atoms with hydrogen and deuterium

Abstract

The gas-phase kinetics of S( 3P) atoms with H 2 and D 2 have been studied via the laser flash photolysis—resonance fluorescence technique. S atoms were generated by pulsed photolysis of CS 2 at 193 nm and monitored by time-resolved fluorescence at 181 nm. The rate coefficients for H 2 ( k 1) and D 2 ( k 2), respectively, are summarized as k 1(600-1110 K) = 3.0 × 10 –9 exp(– 1.317×10 5–2.703×10 7K/ T/ 8.314 T/K ) cm 3 molecule –1 s –1 and k 2(770-1110 K) = 2.2 × 10 –14 ( T/298 K) 3.55 exp(–5420 K/T) cm 3 molecule –1 s –1. Error limits are discussed in the text. The rate coefficients for formation of SH(SD) + H(D) on a newly developed triplet potential energy surface were characterized via ring polymer molecular dynamics and canonical variational transition-state theory. Furthermore there is excellent agreement above about 1000 K between theory and experiment. At lower temperatures, the experimental rate coefficient is substantially larger than the results computed for the adiabatic reaction, suggesting a significant role for intersystem crossing to the singlet potential energy surface at lower temperatures.

Authors:
 [1];  [2]; ORCiD logo [1];  [3];  [4]; ORCiD logo [3]; ORCiD logo [4]
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  1. Univ. of North Texas, Denton, TX (United States)
  2. Univ. of North Texas, Denton, TX (United States); PPG Industries, Gainesville, TX (United States)
  3. Shanghai Univ., Shanghai (China)
  4. Univ. of New Mexico, Albuquerque, NM (United States)
Publication Date:
Research Org.:
Univ. of New Mexico, Albuquerque, NM (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1511685
Alternate Identifier(s):
OSTI ID: 1396315
Grant/Contract Number:  
[SC0015997]
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
[ Journal Volume: 147; Journal Issue: 13]; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Thompson, Kristopher M., Gao, Yide, Marshall, Paul, Wang, Han, Zhou, Linsen, Li, Yongle, and Guo, Hua. Experimental and theoretical studies of the reactions of ground-state sulfur atoms with hydrogen and deuterium. United States: N. p., 2017. Web. doi:10.1063/1.4991418.
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Thompson, Kristopher M., Gao, Yide, Marshall, Paul, Wang, Han, Zhou, Linsen, Li, Yongle, & Guo, Hua. Experimental and theoretical studies of the reactions of ground-state sulfur atoms with hydrogen and deuterium. United States. doi:10.1063/1.4991418.
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Thompson, Kristopher M., Gao, Yide, Marshall, Paul, Wang, Han, Zhou, Linsen, Li, Yongle, and Guo, Hua. Tue . "Experimental and theoretical studies of the reactions of ground-state sulfur atoms with hydrogen and deuterium". United States. doi:10.1063/1.4991418. https://www.osti.gov/servlets/purl/1511685.
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@article{osti_1511685,
title = {Experimental and theoretical studies of the reactions of ground-state sulfur atoms with hydrogen and deuterium},
author = {Thompson, Kristopher M. and Gao, Yide and Marshall, Paul and Wang, Han and Zhou, Linsen and Li, Yongle and Guo, Hua},
abstractNote = {The gas-phase kinetics of S(3P) atoms with H2 and D2 have been studied via the laser flash photolysis—resonance fluorescence technique. S atoms were generated by pulsed photolysis of CS2 at 193 nm and monitored by time-resolved fluorescence at 181 nm. The rate coefficients for H2 (k1) and D2 (k2), respectively, are summarized as k1(600-1110 K) = 3.0 × 10–9 exp(– 1.317×105–2.703×107K/T/ 8.314 T/K ) cm3 molecule–1 s–1 and k2(770-1110 K) = 2.2 × 10–14 (T/298 K)3.55 exp(–5420 K/T) cm3 molecule–1 s–1. Error limits are discussed in the text. The rate coefficients for formation of SH(SD) + H(D) on a newly developed triplet potential energy surface were characterized via ring polymer molecular dynamics and canonical variational transition-state theory. Furthermore there is excellent agreement above about 1000 K between theory and experiment. At lower temperatures, the experimental rate coefficient is substantially larger than the results computed for the adiabatic reaction, suggesting a significant role for intersystem crossing to the singlet potential energy surface at lower temperatures.},
doi = {10.1063/1.4991418},
journal = {Journal of Chemical Physics},
number = [13],
volume = [147],
place = {United States},
year = {2017},
month = {10}
}
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DOI:  10.1063/1.4991418
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Figures / Tables:

FIG. 1. FIG. 1. : Contour plot of the PIP-NN PES in the S–H and H–H′ coordinates in collinear geometry. The transition state is indicated in the figure by a cross, and its geometry is given in the inset. The energy difference between adjacent contours is 0.1 eV.
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