摘要
利用G2(MP2)理论研究了F(2P)与NCO(X2Π)在三重激发态(a3 A″)势能面上的反应机理.揭示了生成NF(X3Σ -)的两种反应途径 ,即顺式和反式加成 -消除.其中顺式反应途径的势垒较低(20.9kJ·mol-1).动力学计算显示 :在室温下 ,F与NCO反应于三重态势能面上只能较缓慢地生成NF(X3Σ -)自由基.预测FC(N)O是另一可能的反应产物.
The reaction of F( 2P) with NCO(X 2Π) on 3A″potential surface has been studied theoretically using G2(MP2) level.Two reaction pathways leading to the NF(X 3Σ-) radicals,i.e.,cis and trans FN addition elimination,were revealed.The cis pathway has the lower entrance energy barrier (20.9 kJ·mol-1).The rate constants were calculated using the transition state theory.It has been shown that the NF(X 3Σ-) radical can be formed directly on the triplet potential energy surface with a slow rate.In addition,the FC(N)O radical was found to be a possible product.
出处
《物理化学学报》
SCIE
CAS
CSCD
北大核心
2000年第6期517-521,共5页
Acta Physico-Chimica Sinica
基金
高等学校博士学科点专项科研基金
关键词
从头算
氟
NCO
氟化氮
反应机理
动力学
Ab initio, Potential energy surface, Addition/elimination, Rate constant, NF(X 3Σ-) radical
