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Ion-molecule reaction mass spectrometry and vacuum-ultraviolet negative photoion spectroscopy

Simpson, Matthew James (2010)
Ph.D. thesis, University of Birmingham.

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Two separate experimental techniques have been used to investigate the fundamental properties of small polyatomic molecules in the gas phase. Selected ion flow tube mass spectrometry has been used to study the reactions of cations and anions with ethene, monofluoroethene, 1,1-difluoroethene, trifluoroethene and tetrafluoroethene. Calculated collisional reaction rate coefficients are compared to those measured by the experiment. The product ions from these reactions have been detected and their branching ratios measured. Many of these results have been explained using arrow-pushing mechanisms. Using tunable vacuum-ultraviolet radiation from a synchrotron, negative ions have been detected following photoexcitation of 24 gaseous molecules. The majority of the molecules studied are halogen-substituted methanes. Product anions resulting from unimolecular ion-pair dissociation reactions were detected, and their ion yields recorded in the range 8-35 eV. Absolute cross sections for ion-pair formation and resulting quantum yields are calculated. This vast collection of data is summarised and ion-pair formation from polyatomic molecules is reviewed.

Type of Work:Ph.D. thesis.
Supervisor(s):Tuckett, Richard Paul
School/Faculty:Colleges (2008 onwards) > College of Engineering & Physical Sciences
Department:School of Chemistry
Additional Information:

A version of this work is published by Springer Verlag:
Two Studies in Gas-Phase Ion Spectroscopy
ISBN 978-3-642-23128-5

Subjects:QD Chemistry
Institution:University of Birmingham
ID Code:1056
This unpublished thesis/dissertation is copyright of the author and/or third parties. The intellectual property rights of the author or third parties in respect of this work are as defined by The Copyright Designs and Patents Act 1988 or as modified by any successor legislation. Any use made of information contained in this thesis/dissertation must be in accordance with that legislation and must be properly acknowledged. Further distribution or reproduction in any format is prohibited without the permission of the copyright holder.
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