CP与C_2H_2^+自由基-离子反应机理与产物分布的理论研究(英文)  

Theoretical investigation regarding the radical-ion reaction mechanism and product distribution of carbon monophosphide CP with acetylene cation C_2H_2^+

作　　者：于海涛[1] 

机构地区：[1]黑龙江大学功能无机材料化学省部共建教育部重点实验室,哈尔滨150080

出　　处：《黑龙江大学自然科学学报》2011年第4期480-489,共10页Journal of Natural Science of Heilongjiang University

基　　金：Supported by the National Natural Science Foundation of China(20301006);the Postdoctoral Research Fund of Heilongjiang Province(20301006)

摘　　要：利用量子化学计算方法对CP与C2H2+的反应机理做了详细的理论研究。计算结果表明,通过动力学有利的反应通道生成的主要产物是HCCCP+。反应是以CP分子的碳原子以无势垒的方式进攻C2H2+的π电子开始的,直接生成1-phosphorous-cyclopropylene阳离子。这个阳离子最后通过C-H键断裂反应生成最终的有利产物HCCCP+。CP+C2H2+的反应机理与CN+C2H2+相似。此外,G2级别的反应能量结果表明,重要的中性分子HCCCX(X=N,P)可以通过HCCCX+(X=N,P)而获得。A detailed mechanism investigation concerning the reaction of CP with C2H2^＋ was performed by means of quantum chemistry methods. The calculated results indicate that the most favorable reaction product is the molecule ion HCCCP^＋ , formed through a dominant reaction pathway in the reaction kinetics of CP ＋ C2H2^＋ , i.e. , a barrierless C - atom attack of CP at the π electron of C2H2^＋ to 1 - phosphorous - cyclopropylene cation followed by a C - H bond dissociation to the final product HCCCP^＋. The reaction mechanism of CP with C2H2^＋ is very similar to that of CN with C2H2. Also, the calculated G2 reaction energies indicate that HCCCX ^＋ （X = N ,P） can be considered as feasible precursors of important neutral molecules HCCCX （X = N,P）.

关 键 词：反应机理 CP分子 乙烯正离子 反应势能面 密度函数理论 

分 类 号：O641.12[理学—物理化学]