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# Vacuum-UV and electron dissociative ionisation studies of SF5Cl

Chim, R. Y. L. and Cicman, P. and Mark, T. and Mayhew, C. A. and Scheier, P. and Tuckett, R. P. (2007) Vacuum-UV and electron dissociative ionisation studies of SF5Cl. International Journal of Mass Spectrometry, 261 (2-3). pp. 208-217. ISSN 1387-3806

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URL of Published Version: http://dx.doi.org/10.1016/j.ijms.2006.09.025

Identification Number/DOI: doi:10.1016/j.ijms.2006.09.025

A complementary study of the interaction of SF$$_5$$Cl in the gas phase with vacuum-UV photons and low-energy electrons from the onset of ionisation, ca. 12 eV, to 20 eV is presented. The photon-induced experiments have used tunable vacuum-UV radiation from a synchrotron and threshold photoelectron photoion coincidence spectroscopy for product ion detection, the electron-induced experiments a trochoidal electron monochromator and a quadrupole mass spectrometer. The strengths and limitations of both experiments are contrasted, the main difference being the absence of state selectivity in the electron-induced study. The parent cation is not observed in either study, suggesting that its ground electronic state is repulsive following Franck-Condon vertical excitation. The fragment cations SF$$_5^+$$, SF$$_4$$Cl$$^+$$, SF$$_4^+$$ and SF$$_3^+$$ have been observed in both studies, with reasonable agreement in their threshold appearance energies. Using a variant of threshold photoelectron photoion coincidence spectroscopy applicable when the ground state of the parent cation is repulsive, the first dissociative ionisation energy of SF$$_5$$Cl is determined to be 12.3 ± 0.2 eV, leading to a value for the adiabatic ionisation energy for the SF$$_5$$ radical of 9.92 ± 0.28 eV. The electron-induced experiment is sensitive to ion-pair production, and onsets for F$$^+$$ and Cl$$^+$$ production have been observed which are only possible energetically if the accompanying fragments are the anions SF$$_4$$Cl$$^-$$ and SF$$_5^-$$, respectively. A lower limit for the electron affinity of the SF$$_4$$Cl radical of 4.88 eV is determined, a value confirmed by ab initio calculations. The electron-induced experiment is very sensitive to gas impurities, and the effects of minute quantities of SF$$_4$$, FCl, Cl$$_2$$ and possibly SF$$_2$$ in the gas sample are observed.

Type of Work: Article 2007 (Publication) Schools (1998 to 2008) > School of Chemical Sciences School of Chemistry, School of Physics Photoionisation ; electron ionisation ; threshold photoelectron and coincidence spectroscopy ; appearance thresholds ; SF5Cl. QD ChemistryQC Physics University of Birmingham Elsevier B.V. 730 YES

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