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Vacuum-Ultraviolet negative photoion spectroscopy of SF5Cl

Simpson, M. J. and Tuckett, R. P. (2010) Vacuum-Ultraviolet negative photoion spectroscopy of SF5Cl. The Journal of Physical Chemistry A, 114. pp. 8043-8048. ISSN 1089-5639

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URL of Published Version: http://dx.doi.org/10.1021/jp105597v

Identification Number/DOI: 10.1021/jp105597v

Using vacuum-UV radiation from a synchrotron, gas-phase negative ions are detected by mass spectrometry following photoexcitation of SF\(_5\)Cl. F\(^-\), Cl\(^-\) and SF\(_5^-\)are observed, and their ion yields recorded in the range 8-30 eV. F\(^-\) and Cl\(^-\) show a linear dependence of signal with pressure, showing that they arise from unimolecular ion-pair dissociation, generically written AB + h\(v\) \(\rightarrow\) C\(^-\) + D\(^+\) (+ neutral(s)). F\(^-\) is the strongest signal, and absolute cross sections are determined by calibrating the signal intensity with that of F\(^-\) from SF\(_6\) and CF\(_4\). Resonances are observed, and assigned to transitions to Rydberg states of SF\(_5\)Cl. The Cl\(^-\) signal is much weaker, despite the S-Cl bond being significantly weaker than the S-F bond. Appearance energies for F\(^-\) and Cl\(^-\) of 12.7 ± 0.2 and 10.6 ± 0.2 eV are determined. The spectra suggest that these ions form indirectly by crossing of Rydberg states of SF\(_5\)Cl onto an ion-pair continuum.

Type of Work:Article
Date:July 2010 (Publication)
School/Faculty:Colleges (2008 onwards) > College of Engineering & Physical Sciences
Department:School of Chemistry
Keywords:sulfur chloropentafluoride ; ion-pair formation ; vacuum-UV ; absolute cross sections
Subjects:QD Chemistry
Institution:University of Birmingham
Copyright Holders:American Chemical Society
ID Code:769
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