Unravelling the dissociation pathways of acetic acid upon electron transfer in potassium collisions: experimental and theoretical studies. Issue 2 (12th December 2016)

• Record Type: Journal Article
• Authors: Meneses, G.; Widmann, C.; Cunha, T.; Gil, A.; Ferreira da Silva, F.; Calhorda, M. J.; Limão-Vieira, P.
• Is Part Of: Physical chemistry chemical physics. Volume 19:Issue 2(2017)
• Page Start: 1083
• Page End: 1088
• Publication Date: 2016-12-12
• Subjects: Chemistry, Physical and theoretical -- Periodicals; 541.3
• DOI: 10.1039/c6cp06375f
• Languages: English
• ISSNs: 1463-9076

Abstract

Abstract : A direct dissociation or concerted mechanism via a diol intermediate, leading to OH − formation in potassium acetic acid collisions? 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 CH3 COOH/CH3 COOD and CD3 COOH 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.