Date of Award

5-2015

Degree Type

Dissertation

Degree Name

Doctor of Philosophy

Major

Chemistry

Major Professor

Michael J. Sepaniak

Committee Members

Sheng Dai, David M. Jenkins, Ramki Kalyanaraman

Abstract

Raman and its associated forms of spectroscopy are powerful tools that have been under-utilized. Presented within are three inorganic compounds studied with some form of Raman spectroscopy: normal Raman, hyper-Raman (HR), surface-enhanced Raman spectroscopy (SERS), surface-enhanced hyper-Raman spectroscopy (SEHRS), or resonance Raman spectroscopy (RR).

The first study involves the investigation of phosphine binding with silver metal. Phosphines find wide use in synthetic circles yet have had little study into their method of binding, unlike similar compounds comprised of sulfur. In order to understand the binding of phosphines, several tertiary phosphines, secondary phosphines and secondary phosphine oxides are examined with SERS. SERS is a surface technique, providing a probe into the surface interaction of the phosphines and silver. By analyzing the results of SERS experiments and using the process of elimination, the secrets of phosphine binding begins to unravel.

The second study involves the use of Raman spectroscopy, along with several other chemistry techniques to characterize a new uranium complex. This particular uranium complex is of interest due to applications to uranium capture and uranium sensing; however, this work did not progress to these points. Detailed in the study are the various facets concerning the complex, using many techniques for characterization.

The third study centers around the investigation of uranium compounds with HR, RR and SEHRS. There are no published works on this subject to the author’s knowledge. Non-linear spectroscopies such as HR offer the benefit of accessing modes forbidden to one-photon spectroscopies, such as traditional linear spectroscopies like Raman and IR. This can lead to new possibilities for identification and sensing not previously accessible.

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