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RRKM Calculations on the Reaction Channels of N(4S)+CH2X(X=F,Cl)
Li Jiang, Zhou Xiaoguo, Pei Linsen, Chen Congxiang, Yu Shuqin*, Ma Xingxiao
Laboratory of Bond-selective Chemistry,Chinese Academy of Science,Department of Chemical Physics,University of Science and Technology of China,Hefei 230026
Abstract:
The microsopic rate constants of N(4S)CH2X(X=F,Cl)reaction have been calculated by RRKM theory . The barrierless dissociation was handled with the loosing transition state model. The results reveal that when activated internal energy is low(280.29 kJ/mol),the major products of N(4S)+CH2F reaction are NCHF+H and H2CN+F,with corresponding branching fraction of 59.2% and 37.4%,respectively . On the other hand,when internal energy is 267.78 kJ / mol,the major products H2CN+Cl give a 90.3% yield of the N(4S)+CH2Cl reaction. When the internal energy is ultra high(500.00 kJ / mol),the main reaction channel is still NCHF+H pathway for the N(4S)+CH2F reaction,while it changes into NCHCl + H for the reaction of N(4S)+CH2Cl,which gives a 51.5% yield,the proportion of H2CN+Cl is reduced to 40.4% .
Key words:  RRKM theory,Nitrogen atom,Halogenated methyl radical,Microsopic rate constant
FundProject:国家重点基础研究基金(G1999075304)和高等学校博士学科点专项科研基金(1999035828) 资助项目.
RRKM理论研究N(4S)+CH2X(X=F,Cl)的反应通道
李江, 周晓国, 裴林森, 陈从香, 俞书勤*, 马兴孝
中国科学院选键化学实验室,中国科学技术大学化学物理系,合肥,230026
摘要:
采用RRKM理论和疏松过渡态模型计算了N(4S)+CH2X(X=F,Cl)反应的微正则速率常数和通道分支比.计算结果表明,在较低的内能下(E=280.29 kJ/mol), N(4S)+CH2F的主要产物为NCHF+H,占总产物的59.2%,次要产物为H2CN+F,占37.4%.而N(4S)+CH2Cl反应在E=267.78 kJ/mol时,主要产物是H2CN+Cl,占90.3%, NCHCl+H只占9.0%.在内能较高的时候(取E=500.00 kJ/mol), N(4S)+CH2F的主要通道并未变化,
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DOI:10.1088/1674-0068/15/3/224-228
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