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DOI	10.1016/j.atmosenv.2020.117833
	Kinetics of hydrogen abstraction from CH3SH by OH radicals: An ab initio RRKM-based master equation study
	Mai T.V.-T.; Nguyen H.T.; Huynh L.K.
发表日期	2020
ISSN	1352-2310
卷号	242
英文摘要	This work presents the mechanism and chemical kinetics for the CH3SH + OH reaction in a broad condition range (200–2000 K & 0.76–760,000 Torr) using the CCSD(T)/aug-cc-pV(T,Q)Z//M06-2X/aug-cc-pV(T+d)Z and Rice–Ramsperger–Kassel–Marcus based master equation (RRKM-ME) calculations. The treatments of the hindered internal rotor (HIR) and tunneling effects were taken into account. The good agreement between our calculated rate constants and experimental values resolves the previous discrepancy between experiment and theory. The reaction mechanism is revealed in detail as: (i) the H-abstraction channel from the thiol (-SH) group is more thermodynamically and kinetically favorable than from the methyl (-CH3) group; (ii) U-shaped temperature-dependent behaviors and weakly positive pressure-dependence at low temperature (T ≤ 500 K) of the rate constants are observed; and (iii) both HIR and tunneling corrections play a role in obtaining reliable rate constants. Besides, the performance of selected chemical quantum methods (i.e., M06-2X, BH&HLYP, B3LYP, and MP2) on the calculated rate constants was examined thoroughly. Furthermore, it is predicted that CH3SH is not a persistent organic pollutant due to its short atmospheric lifetime (~5 h) due to OH radicals and its products (CH2SH and CH3S) can photolyze under the sunlight. © 2020 Elsevier Ltd
关键词	And master equation Atmospheric chemistry Kinetics Methanethiol/methyl mercaptan (CH3SH)OH radicals POPs RRKM
语种	英语
scopus关键词	Calculations; Free radicals; Hydrogen; Kinetics; Organic pollutants; Temperature; Atmospheric lifetime; Experimental values; Hydrogen abstraction; Persistent organic pollutant (POP); Positive pressure; Reaction mechanism; Temperature dependent behavior; Tunneling effects; Rate constants; hydrogen; hydroxyl radical; thiol; detection method; experimental study; hydrogen; hydroxyl radical; methane; persistent organic pollutant; pollutant removal; reaction kinetics; solar radiation; ab initio calculation; Article; atmosphere; atmospheric pressure; chemical reaction kinetics; chemical structure; comparative study; controlled study; low temperature; persistent organic pollutant; photolysis; priority journal; quantum chemistry; rate constant; reaction analysis; sunlight; temperature dependence; thermodynamics
来源期刊	ATMOSPHERIC ENVIRONMENT
文献类型	期刊论文
条目标识符	http://gcip.llas.ac.cn/handle/2XKMVOVA/248913
作者单位	Molecular Science and Nano-Materials Lab, Institute for Computational Science and Technology, SBI Building, Quang Trung Software City, Tan Chanh Hiep Ward, District 12, Ho Chi Minh City, Viet Nam; University of Science, 227 Nguyen Van Cu, Ward 4, District 5, Ho Chi Minh City, Viet Nam; Vietnam National University, Ho Chi Minh, Viet Nam; International University, Quarter 6, Linh Trung Ward, Thu Duc District, Ho Chi Minh City, Viet Nam
推荐引用方式 GB/T 7714	Mai T.V.-T.,Nguyen H.T.,Huynh L.K.. Kinetics of hydrogen abstraction from CH3SH by OH radicals: An ab initio RRKM-based master equation study[J],2020,242.
APA	Mai T.V.-T.,Nguyen H.T.,&Huynh L.K..(2020).Kinetics of hydrogen abstraction from CH3SH by OH radicals: An ab initio RRKM-based master equation study.ATMOSPHERIC ENVIRONMENT,242.
MLA	Mai T.V.-T.,et al."Kinetics of hydrogen abstraction from CH3SH by OH radicals: An ab initio RRKM-based master equation study".ATMOSPHERIC ENVIRONMENT 242(2020).