Dissociative Low-Energy Electron Attachment to the C–S Bond of H3CSCH3 Influenced by Coulomb Stabilization

Abstract

In earlier works by our group, it was suggested that the presence of stabilizing Coulomb potentials can allow low-energy electrons (i.e., with kinetic energies <1 eV) to attach to σ* orbitals of certain bonds and to thus cleave those bonds. In these earlier efforts, we focused on S–S bond cleavage and in breaking a variety of bonds that occur in typical peptides and proteins. In the present effort, we focus primarily on the stabilizing effects of nearby positive charges on the electron attachment process to dimethyl sulfide (DMS) to break one of the C–S bonds. Ab initio electronic structure calculations have been used to explore the influence of Coulomb potentials on the ability of low-energy electrons to directly attach to the σ* orbital of the C–S bond and to effect bond cleavage, as well as to examine σ* anion energy evolution as a function of C–S bond length.