Date of Award

Spring 1-1-2013

Document Type

Dissertation

Degree Name

Doctor of Philosophy (PhD)

Department

Chemistry & Biochemistry

First Advisor

J. Mathias Weber

Second Advisor

G. Barney Ellison

Third Advisor

Neils Damrauer

Fourth Advisor

Carl W. Lineberger

Fifth Advisor

Heather Lewandowski

Abstract

Transition metal complexes play an important role in many aspects of chemistry; whether in supporting biological functions, as catalysts for organic reactions, in the environment, or in industry. This thesis is comprised of gas-phase spectroscopic studies of four transition metal species with implications for many different chemical applications.

Most knowledge of the target molecules in this thesis are derived from studies in the condensed phase, where the chemical environment can change molecular properties. As a result, it is difficult to gain an understanding of the intrinsic properties in solution as well as a molecular-level picture of chemical reactions that take place where many oxidation states, molecular species, and solvent interactions occur. By isolating one particular species in the gas phase, we are able to observe how each species interacts with light independent of perturbing effects of solvent and counter ions.

In this thesis, we perform spectroscopic experiments on mass-selected ions in the gas phase, where we are able to gain information on intrinsic molecular properties without the influence of a condensed phase chemical environment.

We employ photodissociation spectroscopy, where we mass-select a particular ionic species from solution and irradiate that molecular ion with the output of a tunable laser in the ultraviolet and visible regions. By monitoring the fragments produced, we can obtain an electronic absorption spectrum of the isolated species as well as gain insight into the photochemistry of the ions under study from the fragmentation pathways observed. We combine this method with solution absorption spectra as well as electronic structure calculations.

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