利用激光诱导荧光和分子束技术研究反应Ba+SiCl_4、CH_3SiCl_3、C_6H_5SiCl_3  

The Study of the Reactions Ba+SiCl_4,CH_3SiCl_3 C_6H_5SiCl_3 via LIF and Molecular Beam

作　　者：韩克利[1] 莫宇翔[1] 何国钟[1] 楼南泉[1] 

机构地区：[1]中国科学院大连化学物理研究所

出　　处：《Chinese Journal of Chemical Physics》1990年第3期157-161,共5页化学物理学报（英文）

摘　　要：利用LIF方法,在束—气条件下研究了反应Ba+SiCl_4、CH_3SiCl_3、C_6H_5SiCl_3.通过计算机模拟产物BaCl的LIF光谱,以及与反应Ba+CCl_4、CHCl_3、CH_2Cl_2相比较,对反应释能和反应物的对称性在反应中的作用进行了讨论,发现这些反应与反应Ba+CCl_4、CHCl_3、CH_2Cl_2以及某些光解反应有相似的反应机理.并建议反应Ba+C_6H_5SiCl_3有两个反应通道:一个通道是Ba原子的价电子直接进入C_6H_5SiCl_3分子Si-Cl键的反σ轨道,另一个通道是Ba原子的价电子首先进入苯环的反π轨道,反π轨道上的电子通过振动耦合,然后进入Si-Cl的反σ轨道,最终形成BaCl.The reactions of Ba with SiCl_4, CH_3SiCl_3, and C_6H_5SiCl_3 have been studied by means of LIF in a beam-gas equipment. From the LIF spectra of the computer imitated BaCl product, the comparison of the above reactions with that of Ba with CCl_4, CHCl_3 and CH_2Cl_2 and the conclision of our discussion on the role of the released energy of reaction and the symmetry of the reagents in reactions we discovered that both three Ba reactions might possess the similar mechanism of reaction with that of some photolysis reactions. The reaction Ba+C_6H_5SiCl_3 was supposed to proceed via two different mechanisms simultaneously: (1) Atom Ba attacks directly the Si-Cl bond of C_6SiCl_3 leading to form the BaCl product; (2) The valence electron of Ba transfers into the π orbit of benzene ring at first, and then the electron of π orbit of benzene ring transfers into the σ orbit of C-Cl bond via vibrational coupling leading to from the BaCl product.

关 键 词：钡 四氯化硅 氯代硅烷 IF 分子束 

分 类 号：O627.412[理学—有机化学]