M. Pérot-Taillandier, S. Zirah, Q. Enjalbert, R. Antoine, J. Lemoine, P. Dugourd, S. Rebuffat, J.-C. Tabet, and C. Afonso
Chemistry 19 350–357 (2013). DOI

Travail réalisé sur le site de l’Université Paris 6.

Abstract

Electron detachment dissocn. (EDD) and electron photodetachment dissocn. (EPD) are relatively new dissocn. methods that involve electron detachment followed by radical-driven dissocn. from multiply deprotonated species. EDD yields prompt dissocn. whereas only electron detachment is obtained by EPD ; subsequent vibrational activation of the charge-reduced radical anion is required to obtain the product ions. Herein, the fragmentation patterns that were obtained by EDD and by vibrational activation of the charge-reduced radical anions that were produced through EDD or EPD (activated-EDD and activated-EPD) were compared. The obsd. differences were related to the dissocn. kinetics and/or the contribution of electron-induced dissocn. (EID). Time-resolved double-resonance expts. were performed to measure the dissocn. rate consts. of the EDD product ions. Differences in the formation kinetics were revealed between the classical EDD/EPD ’a.i/’’xj complementary ions and some ’a.i/ci/’’’z.j product ions, which were produced with slower dissocn. rate consts., owing to the presence of specific neighboring side chains. A new fragmentation pathway is proposed for the formation of the slow-kinetics ’a.i ions.