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https://hdl.handle.net/2440/17943
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Type: | Journal article |
Title: | Generation of neutrals from anionic precursors in the gas phase: the anionic, neutral and cationic rearrangements of CCCCHO and CCCHCO to HCCCCO |
Author: | Fitzgerald, M. Dua, S. Bowie, J. Mc Anoy, A. |
Citation: | International Journal of Mass Spectrometry, 2003; 228(2-3):467-485 |
Publisher: | Elsevier Science BV |
Issue Date: | 2003 |
ISSN: | 1387-3806 1873-2798 |
Statement of Responsibility: | Mark Fitzgerald, Suresh Dua, John H. Bowie, and Andrew M. McAnoy |
Abstract: | The anions, neutrals and cations of the isomers HCCCCO, CCCHCO and CCCCHO have been studied by experiment and by theory at the CCSD(T)/aug-cc-pVDZ//B3LYP/6-31G(d) level of theory. Anions have been synthesised from precursor neutrals in the source of a mass spectrometer. The anion [HCCCCO]- and (a major proportion of) [CCCHCO]- retain their bond connectivity when energised, but theoretical calculations predict that singlet [CCCCHO]- rearranges to singlet [CCCHCO]- over a barrier of only 28kJmol-1. However, triplet [CCCCHO]- is stable under these conditions. Neutralisation/reionisation of [HCCCCO]- results in the sequential two-electron vertical oxidation [HCCCCO]-→HCCCCO→[HCCCCO]+, with the doublet neutral being stable for the microsecond duration of the NR experiment. In contrast, neutralisation of [CCCHCO]- and [CCCCHO]- yield HCCCCO in rearrangements which occur during or subsequent to neutralisation of the anions. Two-electron oxidation (charge reversal, -CR+) of [CCCHCO]- and [CCCCHO]- both produce the rearranged cation [HCCCCO]+ in exothermic reactions. © 2003 Elsevier Science B.V. All rights reserved. |
Keywords: | Anionic precursors Gas phase Neutrals |
Description: | Copyright © 2003 Elsevier Science B.V. All rights reserved. |
DOI: | 10.1016/S1387-3806(03)00205-7 |
Description (link): | http://www.elsevier.com/wps/find/journaldescription.cws_home/500847/description#description |
Published version: | http://dx.doi.org/10.1016/s1387-3806(03)00205-7 |
Appears in Collections: | Aurora harvest 6 Chemistry publications |
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