A photoelectron and TPEPICO investigation of the acetone radical cation

Emma E. Rennie, Anne Marie Boulanger, Paul M. Mayer, D. M P Holland, David A. Shaw, Louise Cooper, Larisa G. Shpinkova

Research output: Contribution to journalArticle

Abstract

The valence shell photoelectron spectrum, threshold photoelectron spectrum, and threshold photoelectron photoion coincidence (TPEPICO) mass spectra of acetone have been measured using synchrotron radiation. New vibrational progressions have been observed and assigned in the X~ 2B 2 state photoelectron bands of acetone-h6 and acetone-d6, and the influence of resonant autoionization on the threshold electron yield has been investigated. The dissociation thresholds for fragment ions up to 31 eV have been measured and compared to previous values. In addition, kinetic modeling of the threshold region for CH3 ? and CU4 loss leads to new values of 78 ± 2 kJ mol-1 and 75 ± 2 kJ mol-1, respectively, for the 0 K activation energies for these two processes. The result for the methyl loss channel is in reasonable agreement with, but slightly lower than, that of 83 ± 1 kJ mol-1 derived in a recent TPEPICO study by Fogleman et al. The modeling accounts for both low-energy dissociation channels at two different ion residence times in the mass spectrometer. Moreover, the effects of the ro-vibrational population distribution, the electron transmission efficiency, and the monochromator band-pass are included. The present activation energies yield a ?fH298 for CH3CO+ of 655 ± 3 kJ mol-1, which is 4 kJ mol-1 lower than that reported by Fogleman et al. The present ?fW298 for CH3CO+ can be combined with the ? fH298 for CH2CO (-47.5 ± 1.6 kJ mol -1) and H+ (1530 kJ mol-1) to yield a 298 K proton affinity for ketene of 828 ± 4 kJ mol-1, in good agreement with the value (825 kJ mol-1) calculated at the G2 level of theory. The measured activation energy for CH4 loss leads to a ?fH298 (CH2CO+•) of 873 ± 3 kJ mol-1. © 2006 American Chemical Society.

Original languageEnglish
Pages (from-to)8663-8675
Number of pages13
JournalJournal of Physical Chemistry A
Volume110
Issue number28
DOIs
Publication statusPublished - 20 Jul 2006

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acetone
photoelectrons
cations
thresholds
activation energy
dissociation
transmission efficiency
autoionization
monochromators
progressions
mass spectrometers
mass spectra
affinity
synchrotron radiation
ions
electrons
fragments
valence
protons
kinetics

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Rennie, E. E., Boulanger, A. M., Mayer, P. M., Holland, D. M. P., Shaw, D. A., Cooper, L., & Shpinkova, L. G. (2006). A photoelectron and TPEPICO investigation of the acetone radical cation. Journal of Physical Chemistry A, 110(28), 8663-8675. https://doi.org/10.1021/jp0616866
Rennie, Emma E. ; Boulanger, Anne Marie ; Mayer, Paul M. ; Holland, D. M P ; Shaw, David A. ; Cooper, Louise ; Shpinkova, Larisa G. / A photoelectron and TPEPICO investigation of the acetone radical cation. In: Journal of Physical Chemistry A. 2006 ; Vol. 110, No. 28. pp. 8663-8675.
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Rennie, EE, Boulanger, AM, Mayer, PM, Holland, DMP, Shaw, DA, Cooper, L & Shpinkova, LG 2006, 'A photoelectron and TPEPICO investigation of the acetone radical cation', Journal of Physical Chemistry A, vol. 110, no. 28, pp. 8663-8675. https://doi.org/10.1021/jp0616866

A photoelectron and TPEPICO investigation of the acetone radical cation. / Rennie, Emma E.; Boulanger, Anne Marie; Mayer, Paul M.; Holland, D. M P; Shaw, David A.; Cooper, Louise; Shpinkova, Larisa G.

In: Journal of Physical Chemistry A, Vol. 110, No. 28, 20.07.2006, p. 8663-8675.

Research output: Contribution to journalArticle

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T1 - A photoelectron and TPEPICO investigation of the acetone radical cation

AU - Rennie, Emma E.

AU - Boulanger, Anne Marie

AU - Mayer, Paul M.

AU - Holland, D. M P

AU - Shaw, David A.

AU - Cooper, Louise

AU - Shpinkova, Larisa G.

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N2 - The valence shell photoelectron spectrum, threshold photoelectron spectrum, and threshold photoelectron photoion coincidence (TPEPICO) mass spectra of acetone have been measured using synchrotron radiation. New vibrational progressions have been observed and assigned in the X~ 2B 2 state photoelectron bands of acetone-h6 and acetone-d6, and the influence of resonant autoionization on the threshold electron yield has been investigated. The dissociation thresholds for fragment ions up to 31 eV have been measured and compared to previous values. In addition, kinetic modeling of the threshold region for CH3 ? and CU4 loss leads to new values of 78 ± 2 kJ mol-1 and 75 ± 2 kJ mol-1, respectively, for the 0 K activation energies for these two processes. The result for the methyl loss channel is in reasonable agreement with, but slightly lower than, that of 83 ± 1 kJ mol-1 derived in a recent TPEPICO study by Fogleman et al. The modeling accounts for both low-energy dissociation channels at two different ion residence times in the mass spectrometer. Moreover, the effects of the ro-vibrational population distribution, the electron transmission efficiency, and the monochromator band-pass are included. The present activation energies yield a ?fH298 for CH3CO+ of 655 ± 3 kJ mol-1, which is 4 kJ mol-1 lower than that reported by Fogleman et al. The present ?fW298 for CH3CO+ can be combined with the ? fH298 for CH2CO (-47.5 ± 1.6 kJ mol -1) and H+ (1530 kJ mol-1) to yield a 298 K proton affinity for ketene of 828 ± 4 kJ mol-1, in good agreement with the value (825 kJ mol-1) calculated at the G2 level of theory. The measured activation energy for CH4 loss leads to a ?fH298 (CH2CO+•) of 873 ± 3 kJ mol-1. © 2006 American Chemical Society.

AB - The valence shell photoelectron spectrum, threshold photoelectron spectrum, and threshold photoelectron photoion coincidence (TPEPICO) mass spectra of acetone have been measured using synchrotron radiation. New vibrational progressions have been observed and assigned in the X~ 2B 2 state photoelectron bands of acetone-h6 and acetone-d6, and the influence of resonant autoionization on the threshold electron yield has been investigated. The dissociation thresholds for fragment ions up to 31 eV have been measured and compared to previous values. In addition, kinetic modeling of the threshold region for CH3 ? and CU4 loss leads to new values of 78 ± 2 kJ mol-1 and 75 ± 2 kJ mol-1, respectively, for the 0 K activation energies for these two processes. The result for the methyl loss channel is in reasonable agreement with, but slightly lower than, that of 83 ± 1 kJ mol-1 derived in a recent TPEPICO study by Fogleman et al. The modeling accounts for both low-energy dissociation channels at two different ion residence times in the mass spectrometer. Moreover, the effects of the ro-vibrational population distribution, the electron transmission efficiency, and the monochromator band-pass are included. The present activation energies yield a ?fH298 for CH3CO+ of 655 ± 3 kJ mol-1, which is 4 kJ mol-1 lower than that reported by Fogleman et al. The present ?fW298 for CH3CO+ can be combined with the ? fH298 for CH2CO (-47.5 ± 1.6 kJ mol -1) and H+ (1530 kJ mol-1) to yield a 298 K proton affinity for ketene of 828 ± 4 kJ mol-1, in good agreement with the value (825 kJ mol-1) calculated at the G2 level of theory. The measured activation energy for CH4 loss leads to a ?fH298 (CH2CO+•) of 873 ± 3 kJ mol-1. © 2006 American Chemical Society.

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Rennie EE, Boulanger AM, Mayer PM, Holland DMP, Shaw DA, Cooper L et al. A photoelectron and TPEPICO investigation of the acetone radical cation. Journal of Physical Chemistry A. 2006 Jul 20;110(28):8663-8675. https://doi.org/10.1021/jp0616866