RRKM理论研究N(4S)+CH2X(X=F,Cl)的反应通道

RRKM Calculations on the Reaction Channels of N(4S)+CH2X(X=F,Cl)

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,

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% .