Unravelling the dissociation pathways of acetic acid upon electron transfer in potassium collisions: Experimental and theoretical studies

G. Meneses, C. Widmann, T. Cunha, A. Gil, F. Ferreira Da Silva, M. J. Calhorda, P. Limão-Vieira

Research output: Contribution to journalArticle

2 Citations (Scopus)

Abstract

Electron transfer in alkali-molecule collisions with gas phase acetic acid and its deuterated analogues resulting in OH- formation requires considerable internal rearrangement in the temporary negative ion. At a collision energy well above the threshold of negative ion formation, electron transfer from potassium to CH3COOH/CH3COOD and CD3COOH results not only in H transfer from CH3 to COOH/COOD, but also in H release from COOH and subsequent rearrangement to eliminate OH-. These processes are also investigated by theoretical post-Hartree-Fock and DFT calculations. The combination of both studies reveals that the most favourable intermediate mechanism occurs via diol formation. Such intramolecular H transfer is reported here for the first time in the context of electron transfer induced dissociation experiments in alkali-molecule collisions. A comprehensive fragmentation study is presented and dissociation mechanisms are suggested.

Original languageEnglish
Pages (from-to)1083-1088
Number of pages6
JournalPhysical Chemistry Chemical Physics
Volume19
Issue number2
DOIs
Publication statusPublished - 1 Jan 2017

Keywords

  • TEMPORARY ANION STATES
  • SIDE-CHAIN
  • AMINO-ACIDS
  • FORMIC-ACID
  • RADICAL CATIONS
  • IONIZATION

Fingerprint Dive into the research topics of 'Unravelling the dissociation pathways of acetic acid upon electron transfer in potassium collisions: Experimental and theoretical studies'. Together they form a unique fingerprint.

Cite this