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在束-气条件下,利用激光激励化学发光技术,研究了p-轨道电子云空间取向的Ca(~1P_1)与氯代甲烷系列化合物的反应.实验结果表明,Ca(~1P_1)+CH_3Cl的反应具有比较明显的取向效应:当激发态钙原子的p-轨道电子云垂直于钙束运动方向时,CaCl(A~2Ⅱ)及CaCl(B~2∑~+)两通道的反应几率较平行于钙束取向时都有所增加,其中以CaCl(A~2Ⅱ)通道的增加最为显著.随着取代氯原子数目的增多,这一取向效应迅速降低.我们用轨道跟随模型及电子跳跃模型对实验结果进行了解释.另外,本文还获得了Ca(~1P_1)与氯代甲烷反应的绝对化学发光截面及产物分支比.
Under the condition of beam-gas, the reaction of Ca (~ 1P_1) with methyl chloride in p-orbital electron cloud was studied by using laser excitation chemiluminescence technique. The experimental results show that the reaction of Ca (~ 1P_1) + CH_3Cl The reaction has the obvious orientation effect: when the p-orbital electron cloud of the excited calcium atom is perpendicular to the direction of the calcium beam movement, the reaction probability of the two channels of CaCl (A ~ 2Ⅱ) and CaCl The orientation of CaCl2 (A ~ 2Ⅱ) channels increased most rapidly with the increase of the number of substituted chlorine atoms.We used the orbital follow-up model and the electron-hopping model In addition, the absolute chemiluminescence cross section and product branching ratio of Ca (~ 1P_1) reacted with methyl chloride were also obtained.