This review is a continuation of our effort to measure systematically the rate constants for thermal electron capture by bromo-, chloro- and fluoroethans in the mixtures with carbon dioxide using the electron swarm method. All the experimental data show that only two-body reactions occur. The linear dependence of the rate constants (log k) on the electron polarizabilities of the attaching center has been found. Theoretical analysis using PM3 semiempirical method with a commercial HyperChem program were performed and the structure of neutral molecule and its negative ion has been calculated. These results have been compared with the molecular characteristics and thermal electron capture rate constants.
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In this review electron attachment processes in the gas phase are described. Electron attachment occurs when electron in collision with atom or molecule forms negative ion. Usually it is a simple two-body collision but in some particular cases very interested, especially for chemists, multi-body processes occur. The results and the discussion on these multi-body thermal electron capture reactions for three groups of compounds, inorganic hydrides, halocarbons and oxygen containing molecules, are presented. It is demonstrated that in all these compounds the electron attachment by van der Waals complexes is much more efficient than by individual molecules and goes through different mechanisms.
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