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

Authors:
 [1];  [1]; ORCiD logo [1];  [2];  [3]; ORCiD logo [2]; ORCiD logo [3]
  1. Department of Chemistry, University of North Texas, Denton, Texas 76203, USA
  2. Department of Physics, International Center of Quantum and Molecular Structures, and Shanghai Key Laboratory of High Temperature Superconductors, Shanghai University, Shanghai 200444, China
  3. Department of Chemistry and Chemical Biology, University of New Mexico, Albuquerque, New Mexico 87131, USA
Publication Date:
Sponsoring Org.:
USDOE
OSTI Identifier:
1396315
Grant/Contract Number:
SC0015997
Resource Type:
Journal Article: Publisher's Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 147; Journal Issue: 13; Related Information: CHORUS Timestamp: 2018-02-15 02:33:37; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics
Country of Publication:
United States
Language:
English

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. doi:10.1063/1.4991418.
Thompson, Kristopher M., Gao, Yide, Marshall, Paul, Wang, Han, Zhou, Linsen, Li, Yongle, and Guo, Hua. 2017. "Experimental and theoretical studies of the reactions of ground-state sulfur atoms with hydrogen and deuterium". United States. doi:10.1063/1.4991418.
@article{osti_1396315,
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 = {},
doi = {10.1063/1.4991418},
journal = {Journal of Chemical Physics},
number = 13,
volume = 147,
place = {United States},
year = 2017,
month =
}

Journal Article:
Free Publicly Available Full Text
This content will become publicly available on October 3, 2018
Publisher's Accepted Manuscript

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  • The recent detection of molecular anions in the interstellar medium (ISM) has highlighted the need for laboratory studies of negative ion chemistry. Hydrogen atoms are the most abundant atomic species in the ISM, and the chemistry of H atoms with anions may contribute to molecular synthesis in interstellar clouds. This work is a combined experimental and computational study of a series of anions reacting with H atoms by associative detachment (A{sup -} + H {yields} AH + e {sup -}). The anions include deprotonated nitriles (CH{sub 2}CN{sup -}, CH{sub 3}CHCN{sup -}, and (CH{sub 3}){sub 2}CCN{sup -}), acetaldehyde (HC(O)CH{sub 2} {supmore » -}), acetone (CH{sub 3}C(O)CH{sub 2} {sup -}), ethyl acetate (CH{sub 3}CH{sub 2}OC(O)CH{sub 2} {sup -}), methanol (CH{sub 3}O{sup -}), and acetic acid (CH{sub 3}CO{sub 2} {sup -}). Experimental measurements of the reaction rate constants were made with the flowing afterglow-selected ion flow tube technique. Ab initio theoretical calculations were carried out to explore the reaction mechanism and investigate the factors influencing reaction efficiencies, which are largely proportional to reaction exothermicities. Other factors influencing reaction efficiencies include the charge density on the reactive site of the anion, the characteristics of the potential energy surfaces along the approach of the reactants, and angular momentum conservation of the anion-H atom collision.« less
  • Nitrogen-containing organic compounds are important in the interstellar medium (ISM). The detection of some corresponding anions, C{sub n} N{sup -} (n = 1, 3, 5), highlights the importance of laboratory studies of their chemistry, especially with the most abundant atomic species in the ISM, hydrogen atom. This work is a combined experimental and computational study of a series of nitrogen-containing carbanions reacting with H atoms. The anions include C{sub n} N{sup -} (n = 1-6), C{sub n} N{sub 2}{sup -} (n = 1, 3-5), and C{sub n} N{sub 3}{sup -} (n = 2, 4), and reactions mainly proceed through associativemore » detachment (A{sup -} + H {yields} AH + e{sup -}) or fragmentation pathways. Experimental measurements of the reaction rate constants were made with the flowing afterglow-selected ion flow tube technique. Ab initio theoretical calculations were carried out to explore the reaction mechanisms and investigate the factors determining reactivities. Reaction is mainly determined by the characteristics of the potential energy surfaces along the approach of the reactants. In addition, angular momentum conservation of the anion-H atom collision may have the universal effect of decreasing the reaction efficiencies. Our results indicate that C{sub n} N{sup -} (n = 1-6) and C{sub n} N{sub 2}{sup -} (n = 1, 3-5) can be destroyed in reactions with H atoms by either forming the corresponding neutral monohydride compound or fragmenting into smaller anionic and neutral species. However, C{sub n} N{sub 3}{sup -} (n = 2, 4) anions are unreactive, such that they may exist in H atom rich regions in the ISM.« less