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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Chemical and Electronic Branching Ratios in the Chemiluminescent Reactions of Hyperthermal Ca(~3P) Atoms with CF_2Cl_2 and CF_2 = CCl_2
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Chemical and Electronic Branching Ratios in the Chemiluminescent Reactions of Hyperthermal Ca(~3P) Atoms with CF_2Cl_2 and CF_2 = CCl_2

机译：Ca（〜3P）高温与CF_2Cl_2和CF_2 = CCl_2的化学发光反应中的化学和电子支化比

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摘要

Chemiluminescent reactions of hyperthermal Ca(~3P) with CF_2Cl_2 and CF_2 = CCl_2 were studied in a beam-gas arrangement under single collision conditions. Emissions associated with the A(~2Π_Ω) → X(~2∑~+) and the B(~2∑~+) → X(~2∑~+) transitions from CaCl and CaF were observed for both reactions. The chemical and electronic branching ratios were determined for these reactions, and different results were obtained for each one. The different behavior was rationalized by a simple MO pictures. For the case of the reaction with CF_2Cl_2 it was assumed that an electron from Ca(~3P) is transferred to a σ~*(C-Cl) orbital in CF_2Cl_2 which, at higher translational energies can also enter into a σ~*(C-F) orbital of the same molecule. In both cases the molecular anion produced is short-lived and will undergo fast decay to Cl~- or F~- to yield CaCl and CaF. For the reaction with Cf_2 = CCl_2 the electron from Ca(~3P) is transferred to a π~* orbital of the reagent molecule that generates a relatively stable molecular anion with ~2Π symmetry. This anion subsequently cross over several repulsive ~2∑ surfaces associated with σ~* orbitals of the C-Cl and the C-F bonds, to dissociate into Cl~- or F~- to produce CaCl and CaF. The electronic branching ratios are in good agreement with statistical distribution based on information theory approach, assuming the rigid rotor harmonic oscillator (RROH) approximation for the reaction with CF_2Cl_2 and the formation of a collision complex for the reaction with CF_2 = CCl_2.
机译：研究了在单一碰撞条件下束流-气体排列下，高温Ca（〜3P）与CF_2Cl_2和CF_2 = CCl_2的化学发光反应。在两个反应中均观察到与CaCl和CaF的A（〜2Π_Ω）→X（〜2∑〜+）和B（〜2∑〜+）→X（〜2∑〜+）跃迁相关的发射。确定这些反应的化学和电子支化比，并且每个反应获得不同的结果。通过简单的MO图片可以使不同的行为合理化。对于与CF_2Cl_2反应的情况，假定来自Ca（〜3P）的电子转移到CF_2Cl_2中的σ〜*（C-Cl）轨道，该轨道在较高的平移能下也可以进入σ〜*（ CF）同一分子的轨道。在这两种情况下，所产生的分子阴离子都是短寿命的，并且将快速分解为Cl-或F-，从而生成CaCl和CaF。对于与Cf_2 = CCl_2的反应，来自Ca（〜3P）的电子被转移到试剂分子的π〜*轨道上，从而生成具有〜2Π对称性的相对稳定的分子阴离子。该阴离子随后越过几个与C-Cl和C-F键的σ〜*轨道相关的〜2∑排斥表面，分解为Cl〜-或F〜-，生成CaCl和CaF。电子支化比与基于信息论方法的统计分布非常吻合，假定与CF_2Cl_2反应的刚性转子谐波振荡器（RROH）近似，以及与CF_2 = CCl_2反应的碰撞络合物的形成。

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