Dissociative electron attachment to methyl chloride: A quasi-diatomic potential curve for the fragmentation of the metastable CH3Cl- anion

Potential energy curves have been calculated for the dissociation of the neutral CH3Cl molecule and its negative ion into CH3 + Cl and CH3+Cl-, respectively. The neutral molecule and the anion could be treated by means of standard wave function based quantum chemical ab initio methods for C-Cl distances larger than about 2.4 Å, where CH3Cl- is a stable anion. In the present calculation MP3 and CCSD(T) were employed. At shorter C-Cl distances the CH3Cl- anion is only metastable and cannot be treated by such methods. We have applied a stabilization scheme, first proposed by Nestmann and Peyerimhoff, to stabilize the metastable anion by adding extra positive charges to the molecule. By this trick it was possible to generate the resonance energy Eres and width Γ as functions of the C-Cl distance in the resonance regime between 1.5 and 2.5 Å. The calculated values for the threshold energy Ethresh and the exothermicity ΔE0 of the DEA (dissociative electron attachment) process are in very good agreement with experiment; the vertical attachment energy (VAE) is smaller than its experimental counterpart.