Electron-induced chemistry of alcohols

Abstract

We studied dissociative electron attachment (DEA) to a series of compounds with one or two hydroxyl groups. For the monoalcohols we found, apart from the known fragmentations in the 6 — 12 eV range proceeding via Feshbach resonances, also new weaker bands at lower energies, around 3 eV. They have a steep onset at the dissociation threshold and we assigned them as proceeding via shape resonances with temporary occupation of σ*O-H orbitals. These low energy fragmentations become much stronger in the larger molecules and even the strongest DEA process in the compounds with two hydroxyl groups. Above 6 eV, in the Feshbach resonance regime, the dominant process is a fast loss of a hydrogen atom from the hydroxyl group. In some cases the resulting (M — 1)− anion (loss of hydrogen atom) is sufficiently energy-rich to further dissociate by loss of stable, closed shell molecules like H2 or ethene.