Negative ions of ethylene sulfite

Abstract

The formation of negative ions in molecular beams of ethylene sulfite (ES, alternately called glycol sulfite or ethylene glycol, C(2)H(4)SO(3)) molecules has been studied using both Rydberg electron transfer (RET) and free electron attachment methods. RET experiments with jet-cooled ES show an unexpected broad profile of anion formation as a function of the effective quantum number (n(*)) of the excited rubidium atoms, with peaks at n(max)(*) approximately 13.5 and 16.8. The peak at n(max)(*) approximately 16.8 corresponds to an expected dipole-bound anion with an electron binding energy of 8.5 meV. It is speculated that the peak at n(max)(*) approximately 13.5 derives from the formation of a distorted C(2)H(4)SO(3)(-) ion. We suggest that quasifree electron attachment promotes the breaking of one ring bond giving a long-lived acyclic anion and term this process incomplete dissociative electron attachment. Theoretical calculations of plausible ionic structures are presented and discussed. Electron beam studies of ES reveal the presence of multiple dissociative attachment channels, with the dominant fragment, SO(2)(-), peaking at 1.3 eV and much weaker signals due to SO(3)(-), SO(-), and (ES-H)(-) peaking at 1.5, 1.7, and 0.9 eV, respectively. All of these products appear to originate from a broad temporary negative ion resonance centered at approximately 1.4 eV.