Gas Phase Studies of Molecular Clusters Containing Metal Cations, and the Ion Mobility of Styrene Oligomers

This study is divided into three parts. Part I deals with the mechanism of the self-initiated polymerization (or thermal polymerization) of styrene in the gas phase. In this work, we present the first direct evidence for the thermally self-initiated polymerization of styrene in the gas phase. Our approach is based on on-line analysis of the gas phase Oligomers by mass-selected ion mobility. The mobility measurements provide structural information on the ionized oligomers based on their collision cross-sections (Ω) which depend on the geometric shapes of the ions. Theoretical calculations of possible structural candidates of the Oligomers ions are then used to compute angle averaged Ω for comparison with the measured ones. The agreement between the measured and calculated Ω of the candidate structures provides reliable assignments to the structures of the oligomers. Furthermore, collisional-induced dissociations of the mass-selected oligomer ions provide further support for the structures obtained from the mobility measurements. Our results indicate that the gas phase polymerization of styrene proceeds via essentially the same initiation mechanism (the Mayo mechanism) as in condensed phase polymerization. The structural evidence, the mechanism of formation and the observed fragmentation pathway of the growing dimers and trimers in the gas phase are presentedIn Part II the solvation of a variety of metal cations by benzene clusters have been studied using laser vaporization, cluster beam and time-of-flight mass spectrometry techniques. In this work strong magic numbers were observed for clusters containing 10, 13 and 14 benzene molecules depending on the nature of the metal cation involved. The metal cations exhibiting preference solvation by 14 benzene molecules show a strong tendency to form sandwich structures with two benzene molecules. The interpretation of these results in view of the proposed structures and the growth patterns of the clusters are presented. In Part III, the work is focused on the investigation of the intracluster ion molecule reactions following the generation of Mg+ within the polar clusters (water, methanol, ether and acetonitrile).

Name thesis:degree_name

Doctor of Philosophy

Level thesis:degree_level

Dissertation

Discipline thesis:degree_discipline

Chemistry

Year dc:date.available

2004

Author dc:creator

• Alsharaeh, Edreese Housni

Contributors dc:contributor

• Dr. James Terner

• mechanism
• ion mobility mass spectrometry
• TOFMS
• molecular clusters containing metal cations
• CID
• thermal polymerization of styrene
• Chemistry
• Physical Sciences and Mathematics

Statement dc:rights

• © The Author

Identifier

https://scholarscompass.vcu.edu/etd/1200

OAI identifier oai:identifier

oai:scholarscompass.vcu.edu:etd-2199