Issue 24, 2007

Electron-induced chemistry of alcohols


We studied dissociative electron attachment 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 processes at lower energies, around 3 eV. They have a steep onset at the dissociation threshold and show a dramatic D/H isotope effect. 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 the strongest DEA process in the compounds with two hydroxyl groups, which thus represent an intermediate case between the behavior of small alcohols and the sugar ribose which was discovered to have strong DEA fragmentations near zero electron energy [S. Ptasińska, S. Denifl, P. Scheier and T. D. Märk, J. Chem. Phys., 2004, 120, 8505]. 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. The fast primary process is state- and site selective in several cases, the negative ion states with a hole in the nO orbital losing the OH hydrogen, those with a hole in the σC–H orbitals the alkyl hydrogen.

Graphical abstract: Electron-induced chemistry of alcohols

Article information

Article type
28 Mar 2007
24 Apr 2007
First published
24 May 2007

Phys. Chem. Chem. Phys., 2007,9, 3163-3173

Electron-induced chemistry of alcohols

B. C. Ibănescu, O. May, A. Monney and M. Allan, Phys. Chem. Chem. Phys., 2007, 9, 3163 DOI: 10.1039/B704656A

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity