Articles you may be interested inDipolebound excited states of the I−CH3CN and I−(CH3CN)2 ion-molecule complexes: Evidence for asymmetric solvation Laser induced fluorescence measurements of the X 2Σ+ state of CN produced by electron impact on CH3CN J. Chem. Phys. 95, 754 (1991);Thermal electron attachment to nitromethane, methylcyanide, methyliodide, and methylbromide is compared with capture of electrons by these molecules from highly excited Rydberg states of atoms. Data on thermal electron attachment to CH 3 NO, are consistent with a three-body attachment process, with the nature of the third body being important. The thermal energy electron attachment rate constant for CH 3 CN is :s; 1.24X 10-" cm 3 sec-I. Some results on dissociative electron attachment and io~ pairing processes in CH 3 N0 2 , CH 3 CN, CH 3 I, and CH3Br are also presented.
Dissociative-electron-attachment cross sections (some unpublished) for 30 molecules are summarized, evaluated, and discussed within the framework of the resonance scattering theory. The dissociative-attachment peak cross section, σc(εmax), is found to be a strong function of the peak (resonance) energy, εmax, with a break in this dependence at the energy where electronic excitation of the neutral molecule begins to occur. Based on the experimental data, three groups of molecules have been distinguished: (i) those where εmax is less than the energy, εN, of known electronic excited states of the neutral molecule, and the negative-ion state is purely repulsive in the Franck-Condon region, (ii) those where εmax ≥ εN, and (iii) those with exceptionally small σc(εmax) for which a vertical onset for dissociative attachment occurs. For the molecules in group (i) σc(εmax) varies almost as (εmax)−1, while for group (ii) σc(εmax) is a much stronger decreasing function of the resonance energy εmax. For group (i) the effect of autoionization on σc(εmax) is small, and isotopic effects on σc(εmax) are contained within the square root of the inverse ratio of the reduced masses of the products. For group (ii) and especially group (iii) the effect of autoionization on σc(εmax) is large and so are the isotopic effects on σc(εmax).
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