氟代乙炔的氟迁移重排反应动态学和产物振动态分布  

KINETICS AND PRODUCT VIBRATIONAL STATE DISTRIBUTIONS OF THE F SHIFT REARRANGEMENT REACTION OF FLUOROACETYLENE

作　　者：吴俊南[1] 刘成俊[1] 李宗和[1] 王艳[1] 王梅天[1] 

机构地区：[1]北京师范大学化学系,山西医学院药学系

出　　处：《北京师范大学学报（自然科学版）》1994年第4期499-503,共5页Journal of Beijing Normal University(Natural Science)

基　　金：国家自然科学基金

摘　　要：用从头算方法，获得了氟迁移重排反应的内禀反应坐标（ＩＲＣ）．沿着ＩＲＣ，计算了各简正模所对应的频率（ω）以及沿ＩＲＣ运动与垂直于ＩＲＣ运动的简正模之间的耦合常数（Ｂｋ，ｆ）；根据传统过渡态、变分过渡态理论及相应的隧道效应校正，计算了本反应的反应速率常数；使用统一的半经典微扰和无限级突然近似（ＳＣＰ－ＩＯＳ）理论，得到了在一定能量下产物的振动态分布．结果表明在过渡态后Ｂｋ，ｆ的大小直接影响产物振动态的几率分布。The intrinsic reaction coordinate(IRC)of the F shift rearrangement reaction are traced at the SCF MO/STO-3G level.Along the IRC,the vibrational frequencies of normal modes and the coupling constants(Bk,f,)between the IRC and other normal modes are calculated.According to conventional transition state theory,variational transition state theory and tunneling corrections,the reaction rate constants of this rearrangement reaction are obtained. In addition,the vibrational state distributions of this reaction are investigated under different energies by using the semiclassical perturbation(SCP)approximation and the infinite order sudden(IOS)approximation.The calculated results show that when the reaction coordinate S>0 the magnitude of coupling constants(Bk,f,)will notably affected the distribution probabilities of vibrational states of the product.

关 键 词：氟代乙炔 重排反应 振动态分布 氟 迁移 

分 类 号：O623.225[理学—有机化学]