Electron-capture reactions of multiply charged polycyclic aromatic ions

Kingston, R. G.; Brenton, A.G.; Beynon, J. H.

doi:10.1016/0168-1176(87)87009-x

Cited by 5 publications

(2 citation statements)

References 20 publications

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“…Finally, our results are in agreement with previous studies [24][25][26] on systems of about the same size, about the way the internal energy of the monocations varies with the exothermicity or endothermicity of the charge transfer process. Low ionisation energy target gases lead to an exothermic process and favour large internal energies.…”

Section: Discussionsupporting

confidence: 93%

“…20 Molecular systems of medium size have, however, received much less attention. [21][22][23][24][25][26][27] In line with previous work, 15,27 we will focus in this paper on a specific kind of collisional charge transfer, i.e. the single electron capture (SEC) between doubly-charged cations and various target gases at kiloelectronvolt collision energies.…”

Section: Introductionmentioning

confidence: 91%

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Charge Exchange in Tandem Mass Spectrometry: Dissociative Single Electron Capture by Doubly-Charged Toluene Cations

Fati

Leyh

2003

Eur J Mass Spectrom (Chichester)

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Single electron capture by doubly-charged toluene cations upon collision with various target gases has been investigated by sector tandem mass spectrometry. Both non-dissociative and dissociative charge transfer reactions leading to C(7)H(7)(+) + H and to C(5)H(5)(+) + [C(2),H(3)] are detected. Seven atomic or molecular target gases have been used with ionisation energies ranging from 8.8 eV to 14 eV. The branching ratios between the different non-dissociative and dissociative exit channels have been determined as well as the translational energy release on the dissociation products. The experimental data are compared to the predictions of a two-state semi-classical theoretical model that takes into account the non-adiabatic transition responsible for the charge transfer reaction. A wide reaction window shows up but the internal energies of the C(7)H(8)(+) cations produced by single electron capture are observed to be larger than expected. We assign this effect partly to the influence of the large density of vibrational states and to the multichannel nature of the process. Excited states of the dication are also most probably involved in the charge exchange reaction.

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Section: Discussionsupporting

confidence: 93%

Section: Introductionmentioning

confidence: 91%

Charge Exchange in Tandem Mass Spectrometry: Dissociative Single Electron Capture by Doubly-Charged Toluene Cations

Fati

Leyh

2003

Eur J Mass Spectrom (Chichester)

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Collision‐induced fragmentation reactions of doubly charged ions of polycyclic aromatic hydrocarbons

Sim¹,

Jamieson²,

Boyd³

1989

Org. Mass Spectrom.

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Unimolecular and collision-induced reactions of molecular dications M2 + of polycyclic aromatic hydrocarbons (PAHs) have been investigated. For larger PAHs (three or more rings) charge-separation reactions, and both dissociative and non-dissociative electroncapture collisions, are less important. In both low energy (0-400 eV) and high energy (16 kev) collision regimes, the dominant processes are expulsion of hydrogen atoms and of neutral acetylene molecules. In the high-energy collision regime, neutral free radicals are also expelled from these M2+ precursors. Some degree of isomer differentiation is possible via relative intensities of doubly charged fragment ions in the low-energy collision regime, but not all isomers can be thus distinguished and it seems unlikely that such a scheme could be made predictive. The CID spectra are largely independent of precursor size or structure at lower masses (m/z < 70). These findings are reviewed in the light of literature data on expulsion of small neutral species from aromatic dications. It is proposed that the charge-separation reactions characteristic of smaller aromatic systems are charge-site-initiated cleavages, while expulsion of small neutral species such as acetylene is a radicalsite-initiated reaction from M3+ ions possessing considerable diradical character. In all cases an important driving force is the avoidance of anti-aromatic character for a benzene ring from which two electrons have been removed. The similarity of the CID spectra at low masses is analogous to that discussed recently (S. J. Pachuta et al., J. Am. Chem. SOC. 110,657 (1988)) for fragmentations of the corresponding singly charged molecular radical cations.

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CH5N2 hydrazyl radicals, cations and dication radicals studied by mass spectrometry. Is the N-protonated formaldehyde hydrazon cation +CH2NHNH2 a bridged species?

Burgers¹,

Drewello

Schwarz

et al. 1989

International Journal of Mass Spectrometry and Ion Processes

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Electron-capture reactions of multiply charged polycyclic aromatic ions

Cited by 5 publications

References 20 publications

Charge Exchange in Tandem Mass Spectrometry: Dissociative Single Electron Capture by Doubly-Charged Toluene Cations

Charge Exchange in Tandem Mass Spectrometry: Dissociative Single Electron Capture by Doubly-Charged Toluene Cations

Collision‐induced fragmentation reactions of doubly charged ions of polycyclic aromatic hydrocarbons

CH5N2 hydrazyl radicals, cations and dication radicals studied by mass spectrometry. Is the N-protonated formaldehyde hydrazon cation +CH2NHNH2 a bridged species?

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