Electronic Theses and Dissertations

Date of Award

2016

Document Type

Dissertation

Degree Name

Ph.D. in Chemistry

Department

Chemistry and Biochemistry

First Advisor

Nathan Hammer

Second Advisor

Joseph R. Gladden

Third Advisor

Jason Ritchie

Relational Format

dissertation/thesis

Abstract

The underlying motivation of chemical physics and physical chemistry is to understand naturally occurring chemical and physical processes from the nanoscopic molecular level to the macroscopic condensed phase. Over the past half-century, experimentalists have developed a number of laser-based analytical techniques to bridge the gap between the bulk phase and the single molecule. Here, we look at bulk phase and gas phase clusters to compare the local hydrogen-bonded network. To better understand the role noncovalent interactions have on biologically relevant building blocks in a natural environment, we compare the microhydration of gas phase cluster ions to condensed phase spectra. The accommodation of excess charge plays an essential character in a number of biochemical processes involving peptides, nucleobases, aerosols, etc. A time-of-flight mass spectrometer was constructed to isolate discrete numbers of solute and solvent molecules for spectroscopic interrogation via light-matter interactions. We also employed high-resolution Raman spectroscopy for vibrational interrogation of temperature dependence in crystalline lattice modes as well as effects of surface-enhanced Plasresonances. Electronic structure methods were employed for accurate spectral assignment and identification of structural motifs.

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