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 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.
- Authors:
-
- Univ. of North Texas, Denton, TX (United States)
- Univ. of North Texas, Denton, TX (United States); PPG Industries, Gainesville, TX (United States)
- Shanghai Univ., Shanghai (China)
- 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.
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. https://doi.org/10.1063/1.4991418
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. https://doi.org/10.1063/1.4991418. https://www.osti.gov/servlets/purl/1511685.
@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}
}
Web of Science
Figures / Tables:

Works referenced in this record:
Simplified CCSD(T)-F12 methods: Theory and benchmarks
journal, February 2009
- Knizia, Gerald; Adler, Thomas B.; Werner, Hans-Joachim
- The Journal of Chemical Physics, Vol. 130, Issue 5
A kinetic study of the recombination reaction sodium + sulfur dioxide + argon
journal, February 1991
- Shi, Youchun; Marshall, Paul
- The Journal of Physical Chemistry, Vol. 95, Issue 4
Nitrogen sulphur interactions in coal flames
journal, May 2001
- Hampartsoumian, E.; Nimmo, W.; Gibbs, B. M.
- Fuel, Vol. 80, Issue 7
Statistical mechanics of isomerization dynamics in liquids and the transition state approximation
journal, January 1978
- Chandler, David
- The Journal of Chemical Physics, Vol. 68, Issue 6
Representing Global Reactive Potential Energy Surfaces Using Gaussian Processes
journal, March 2017
- Kolb, Brian; Marshall, Paul; Zhao, Bin
- The Journal of Physical Chemistry A, Vol. 121, Issue 13
Permutation invariant polynomial neural network approach to fitting potential energy surfaces
journal, August 2013
- Jiang, Bin; Guo, Hua
- The Journal of Chemical Physics, Vol. 139, Issue 5
Kinetics of the High-Temperature H2S Decomposition
journal, December 1994
- Woiki, D.; Roth, P.
- The Journal of Physical Chemistry, Vol. 98, Issue 49
Kinetics of the thermal decomposition of hydrogen sulfide behind shock waves
journal, January 1977
- Bowman, Craig T.; Dodge, Lee G.
- Symposium (International) on Combustion, Vol. 16, Issue 1
UV Absorption Study of the Thermal Decomposition Reaction H2S .fwdarw. H2 + S(3P)
journal, December 1994
- Olschewski, H. A.; Troe, J.; Wagner, H. Gg.
- The Journal of Physical Chemistry, Vol. 98, Issue 49
Time-dependent Wave Packet Quantum Scattering Study of Reaction S( 3 P)+H 2 →HS+H on a New ab initio Potential Energy Surface 3 A′
journal, June 2012
- Lv, Shuang-jiang; Zhang, Pei-yu; He, Guo-zhong
- Chinese Journal of Chemical Physics, Vol. 25, Issue 3
Quantum statistics and classical mechanics: Real time correlation functions from ring polymer molecular dynamics
journal, August 2004
- Craig, Ian R.; Manolopoulos, David E.
- The Journal of Chemical Physics, Vol. 121, Issue 8
Derivation of a true ( t → 0 + ) quantum transition-state theory. I. Uniqueness and equivalence to ring-polymer molecular dynamics transition-state-theory
journal, February 2013
- Hele, Timothy J. H.; Althorpe, Stuart C.
- The Journal of Chemical Physics, Vol. 138, Issue 8
S 2 Formation during the Pyrolysis of H 2 S in Shock Waves
journal, April 1976
- Higashihara, Tetsuo; Saito, Ko; Yamamura, Hitoshi
- Bulletin of the Chemical Society of Japan, Vol. 49, Issue 4
Thermal decomposition of hydrogen sulfide at low concentrations
journal, January 1982
- Roth, P.; Löhr, R.; Barner, U.
- Combustion and Flame, Vol. 45
Studies on the Reactions of Atomic Sulfur ( 3 P) with H 2 , D 2 , CH 4 , C 2 H 6 , C 3 H 8 , n -C 4 H 10 , and i -C 4 H 10
journal, January 1996
- Tsuchiya, Kentaro; Yamashita, Koichi; Miyoshi, Akira
- The Journal of Physical Chemistry, Vol. 100, Issue 43
Bimolecular reaction rates from ring polymer molecular dynamics
journal, May 2009
- Collepardo-Guevara, Rosana; Suleimanov, Yury V.; Manolopoulos, David E.
- The Journal of Chemical Physics, Vol. 130, Issue 17
Bimolecular reaction rates from ring polymer molecular dynamics: Application to H + CH 4 → H 2 + CH 3
journal, January 2011
- Suleimanov, Yury V.; Collepardo-Guevara, Rosana; Manolopoulos, David E.
- The Journal of Chemical Physics, Vol. 134, Issue 4
Derivation of a true ( t → 0 + ) quantum transition-state theory. II. Recovery of the exact quantum rate in the absence of recrossing
journal, August 2013
- Althorpe, Stuart C.; Hele, Timothy J. H.
- The Journal of Chemical Physics, Vol. 139, Issue 8
Exact quantum scattering study of the H + HS reaction on a new ab initio potential energy surface H 2 S ( 3 A ″ )
journal, March 2012
- Lv, Shuang-Jiang; Zhang, Pei-Yu; Han, Ke-Li
- The Journal of Chemical Physics, Vol. 136, Issue 9
Ring polymer molecular dynamics with surface hopping
journal, December 2012
- Shushkov, Philip; Li, Richard; Tully, John C.
- The Journal of Chemical Physics, Vol. 137, Issue 22
Kinetic Studies on the Pyrolysis of H 2 S
journal, January 1996
- Shiina, Hiroumi; Oya, Masaaki; Yamashita, Koichi
- The Journal of Physical Chemistry, Vol. 100, Issue 6
An experimental and computational study of the reaction of ground-state sulfur atoms with carbon disulfide
journal, October 2011
- Gao, Yide; Marshall, Paul
- The Journal of Chemical Physics, Vol. 135, Issue 14
RPMDrate: Bimolecular chemical reaction rates from ring polymer molecular dynamics
journal, March 2013
- Suleimanov, Yu. V.; Allen, J. W.; Green, W. H.
- Computer Physics Communications, Vol. 184, Issue 3
A shock tube study of the reaction S + H2 ? SH + H in pyrolysis and photolysis systems
journal, June 1995
- Woiki, D.; Roth, P.
- International Journal of Chemical Kinetics, Vol. 27, Issue 6
Rigorous formulation of quantum transition state theory and its dynamical corrections
journal, December 1989
- Voth, Gregory A.; Chandler, David; Miller, William H.
- The Journal of Chemical Physics, Vol. 91, Issue 12
Chemical Reaction Rate Coefficients from Ring Polymer Molecular Dynamics: Theory and Practical Applications
journal, September 2016
- Suleimanov, Yury V.; Aoiz, F. Javier; Guo, Hua
- The Journal of Physical Chemistry A, Vol. 120, Issue 43
Kinetic studies and ab initio investigations of the reactions of atomic bromine with methylsilane and dimethylsilane
journal, January 1993
- Ding, Luying; Marshall, Paul
- Journal of the Chemical Society, Faraday Transactions, Vol. 89, Issue 3
Significant Nonadiabatic Effects in the S( 1 D) + HD Reaction
journal, August 2007
- Chu, Tian-Shu; Han, Ke-Li; Schatz, George C.
- The Journal of Physical Chemistry A, Vol. 111, Issue 34
Communication: Nonadiabatic ring-polymer molecular dynamics
journal, July 2013
- Richardson, Jeremy O.; Thoss, Michael
- The Journal of Chemical Physics, Vol. 139, Issue 3
Importance of Intersystem Crossing in the S( 3 P, 1 D) + H 2 → SH + H Reaction †
journal, October 2004
- Maiti, Biswajit; Schatz, George C.; Lendvay, György
- The Journal of Physical Chemistry A, Vol. 108, Issue 41
Investigation on the Insertion Channel in the S( 3 P) + H 2 Reaction
journal, May 1998
- Shiina, Hiroumi; Miyoshi, Akira; Matsui, Hiroyuki
- The Journal of Physical Chemistry A, Vol. 102, Issue 20
Potential energy surfaces from high fidelity fitting of ab initio points: the permutation invariant polynomial - neural network approach
journal, July 2016
- Jiang, Bin; Li, Jun; Guo, Hua
- International Reviews in Physical Chemistry, Vol. 35, Issue 3
Quantum-classical crossover of the transition rate in the damped double well
journal, August 1987
- Gillan, M. J.
- Journal of Physics C: Solid State Physics, Vol. 20, Issue 24
Kinetic Study of the Pyrolysis of H 2 S
journal, August 2003
- Binoist, Manuel; Labégorre, Bernard; Monnet, Franck
- Industrial & Engineering Chemistry Research, Vol. 42, Issue 17
Direct dynamics calculation of the kinetic isotope effect for an organic hydrogen-transfer reaction, including corner-cutting tunneling in 21 dimensions
journal, August 1993
- Liu, Yi Ping; Lu, Da Hong; Gonzalez-Lafont, Angels
- Journal of the American Chemical Society, Vol. 115, Issue 17
Ring-Polymer Molecular Dynamics: Quantum Effects in Chemical Dynamics from Classical Trajectories in an Extended Phase Space
journal, April 2013
- Habershon, Scott; Manolopoulos, David E.; Markland, Thomas E.
- Annual Review of Physical Chemistry, Vol. 64, Issue 1
Rate coefficients for S( 1 D ) removal at 300 K
journal, January 1985
- Black, G.; Jusinski, L. E.
- The Journal of Chemical Physics, Vol. 82, Issue 2
Variational Transition State Theory
journal, October 1984
- Truhlar, D. G.; Garrett, B. C.
- Annual Review of Physical Chemistry, Vol. 35, Issue 1
Bridging the gap between thermodynamic integration and umbrella sampling provides a novel analysis method: “Umbrella integration”
journal, October 2005
- Kästner, Johannes; Thiel, Walter
- The Journal of Chemical Physics, Vol. 123, Issue 14
Evaluated Chemical Kinetic Rate Constants for Various Gas Phase Reactions
journal, January 1973
- Schofield, Keith
- Journal of Physical and Chemical Reference Data, Vol. 2, Issue 1
An efficient ring polymer contraction scheme for imaginary time path integral simulations
journal, July 2008
- Markland, Thomas E.; Manolopoulos, David E.
- The Journal of Chemical Physics, Vol. 129, Issue 2
Kinetically constrained ring-polymer molecular dynamics for non-adiabatic chemical reactions
journal, February 2014
- Menzeleev, Artur R.; Bell, Franziska; Miller, Thomas F.
- The Journal of Chemical Physics, Vol. 140, Issue 6
Accurate Determination of Tunneling-Affected Rate Coefficients: Theory Assessing Experiment
journal, July 2017
- Zuo, Junxiang; Xie, Changjian; Guo, Hua
- The Journal of Physical Chemistry Letters, Vol. 8, Issue 14
Chemical reaction rates from ring polymer molecular dynamics
journal, February 2005
- Craig, Ian R.; Manolopoulos, David E.
- The Journal of Chemical Physics, Vol. 122, Issue 8
Hidden interactions—Trace species governing combustion and emissions
journal, January 2007
- Glarborg, Peter
- Proceedings of the Combustion Institute, Vol. 31, Issue 1
Kinetics of hydrogen-transfer isomerizations of butoxyl radicals
journal, January 2010
- Zheng, Jingjing; Truhlar, Donald G.
- Physical Chemistry Chemical Physics, Vol. 12, Issue 28
A refined ring polymer molecular dynamics theory of chemical reaction rates
journal, July 2005
- Craig, Ian R.; Manolopoulos, David E.
- The Journal of Chemical Physics, Vol. 123, Issue 3
Reaction kinetics of the addition of atomic sulfur to nitric oxide
journal, November 2004
- Goumri, A.; Shao, Diane D.; Marshall, Paul
- The Journal of Chemical Physics, Vol. 121, Issue 20
Kinetically Constrained Ring-Polymer Molecular Dynamics for Non-adiabatic Chemical Reactions
text, January 2014
- Menzeleev, Artur R.; Bell, Franziska; Miller, Thomas F.
- arXiv
Works referencing / citing this record:
Rate coefficients of the H + H 2 O 2 → H 2 + HO 2 reaction on an accurate fundamental invariant-neural network potential energy surface
journal, November 2018
- Lu, Xiaoxiao; Meng, Qingyong; Wang, Xingan
- The Journal of Chemical Physics, Vol. 149, Issue 17
Figures / Tables found in this record: