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Theoretical Study on Gas Phase Reactions of OH Hydrogen-Abstraction from Formyl Fluoride with Di erent Catalysts
Ding-mei Wang,Zheng-wen Long,Xing-feng Tan,Bo Long,Wei-jun Zhang
Author NameAffiliationE-mail
Ding-mei Wang Department of Physics, Guizhou University, Guiyang 550025, China  
Zheng-wen Long Department of Physics, Guizhou University, Guiyang 550025, China  
Xing-feng Tan College of Computer and Information Engineering, Guizhou MinZu University, Guiyang 550025, China  
Bo Long College of Computer and Information Engineering, Guizhou MinZu University, Guiyang 550025, China wwwltcommon@sina.com 
Wei-jun Zhang Laboratory of Environment Spectroscopy, Anhui Institute of Optics and Fine Mechanics, Chinese Academy of Sciences, Hefei 230031, China;Key Laboratory of Atmospheric Composition and Optical Radiation, Anhui Institute of Optics and Fine Mechanics, Chinese Academy of Sciences, Hefei 230031, China wjzhang@aiofm.ac.cn 
Abstract:
The mechanisms and kinetics of the gas phase reactions that the hydrogen atom in formyl uoride (FCHO) abstracted by OH in the presence of water, formic acid (FA), or sulfuric acid (SA) are theoretically investigated at the CCSD(T)/6-311++G(3df, 3pd)//M06-2X/6-311++G(3df, 3pd) level of theory. The calculated results show that the barriers of the transition states involving catalysts are lowered to -2.89, -6.25, and -7.76 kcal/mol from 3.64 kcal/mol with respect to the separate reactants, respectively, which re ects that those catalysts play an important role in reducing the barrier of the hydrogen abstraction reaction of FCHO with OH. Additionally, using conventional transition state theory with Eckart tun-neling correction, the kinetic data demonstrate that the entrance channel X FCHO+OH (X=H2O, FA, or SA) is signi cantly more favorable than the pathway X OH+FCHO. More-over, the rate constants of the reactions of FCHO with OH radical with H2O, FA, or SA introduced are computed to be smaller than that of the naked OH+FCHO reaction because the concentration of the formed X FCHO or X OH complex is quite low in the atmosphere.
Key words:  Formyl uoride  Hydrogen abstraction  Reaction mechanisms  Rate constants
FundProject:This work was supported by the National Natu-ral Science Foundation of China (No.41165007 and No.21163003), the Science and Technology Founda-tion of Guizhou Province of China (No.[2011]2107 and No.[2012]2189), and the Science and Technology Foun-dation of Guizhou Province of Guizhou Minzu Univer-sity of China (No.[2014]7380).
气相中自由基OH在不同催化剂下对甲酰氟FCHO进行提氢反应的理论性研究
王定美,隆正文,谭兴凤,龙波,张为俊
摘要:
分别在水、甲酸和硫酸存在的情况下,通过CCSD(T)//M06-2X/6-311++G(3df,3pd)的理论方法,对大气中自由基OH提取甲酰氟FCHO上的氢进行了反应机理和动力学的研究.计算结果表明相对于反应物,加入催化剂的过渡态的能垒从3.64 kcal/mol分别下降到-2.89、-6.25和-7.76 kcal/mol,表明水、甲酸和硫酸在甲酰氟FCHO和自由基OH提氢反应中起了重要作用.通过运用具有Eckart隧道校正的传统过渡态理论计算出的动力学数据表明通道X...FCHO+OH(X=H2O, HCOOH,或者H2SO4)要比通道X...OH+FCHO更有利于反应的发生.催化剂水、甲酸和硫酸的加入使甲酰氟FCHO 和自由基OH提氢反应的速率常数要比不加催化剂时小,说明了催化剂的加入不能促进大气中甲酰氟FCHO和自由基OH的反应.
关键词:  甲酰氟FCHO  提氢反应  反应机理  速率常数
DOI:10.1063/1674-0068/29/cjcp1509187
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