Photodissociation studies of gas phase metal ion-molecule complexes
Grieves, Gregory Alan
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A survey of metal ion-molecule complexes produced by pulsed laser vaporization and studied in the gas phase is presented. The technique of laser vaporization is explored for its utility in generating important and interesting complexes. The rst systematic application of this method for producing doubly charged metal ion solvation complexes is reported. Certain multiply charged clusters are thermodynamically unstable to charge transfer at long range, yet these were also able to be generated. A consistent criterion to determine which of the unstable complexes could be produced is the proximity of the degeneracy point of the doubly charged state with the charge transfer state, which has important implications for solvation e ects in these clusters. Fixed frequency photodissociation can provide important clues to the structure of metal clusters where spectroscopic techniques fail. Application of xed frequency photodissociation to novel extended structures of lanthanide metalcyclooctatetraene complexes is demonstrated. Patterns in the dissociation products indicate that these clusters form extended multi-decker \sandwich" type structures with up to three ligand layers. Infrared photodissociation spectroscopy is a powerful tool for studies of model systems of metal ion solvation in the gas phase. Utilizing this technique, nickel ions clustered with carbon dioxide distinctly show signatures of ligand shell layering. The rst coordination sphere of nickel with carbon dioxide was demonstrated to exist at four carbon dioxide molecules. Results indicate a solventinduced intracluster reaction occurs in the clusters producing a multiply charged nickel core while immersed in a carbon dioxide cluster.