物理化学学报 >> 2000, Vol. 16 >> Issue (06): 517-521.doi: 10.3866/PKU.WHXB20000608

研究论文 上一篇    下一篇

F+NCO反应的机理和动力学

侯华, 王宝山, 顾月姝   

  1. 山东大学化学系，济南 250100
  • 收稿日期:1999-10-26 修回日期:2000-01-13 发布日期:2000-06-15
  • 通讯作者: 顾月姝 E-mail:guojz@icm.sdu.edu.cn

Mechanism and Kinetics of the F+NCO Reaction

Hou Hua, Wang Bao-Shan, Gu Yue-Shu   

  1. School of Chemistry,Shandong University,Jinnan 250100
  • Received:1999-10-26 Revised:2000-01-13 Published:2000-06-15
  • Contact: Gu Yue-Shu E-mail:guojz@icm.sdu.edu.cn

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摘要：

利用G2(MP2)理论研究了F(2P)与NCO(X 2Π)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.

关键词: 从头算, 势能面, 加成-消除, 速率常数, NF自由基

Abstract:

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 F→N 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.

Key words: Ab initio, Potential energy surface, Addition/elimination, Rate constant, NF(X3Σ-) radical