Title | Unravelling the dissociation pathways of acetic acid upon electron transfer in potassium collisions: experimental and theoretical studies. |
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Authors | Meneses, G.; Widmann, C.; Cunha, T.; Gil, A.; da Silva, F.; Calhorda, M.J.; Limão-Vieira, P. |
Journal | Phys Chem Chem Phys |
DOI | 10.1039/c6cp06375f |
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. |
Unravelling the dissociation pathways of acetic acid upon electron transfer in potassium collisions: experimental and theoretical studies.