| Description |
The primary aim of this dissertation is to determine and explain the fundamental characteristics of hydrogen-bonded and floppy systems through the development of advanced rovibrational spectroscopic models. In particular, this dissertation has focused on deciphering the rovibrational signatures involved in ion/radical hydration through the development and application of new computational methodologies. Ion hydration is ubiquitous in many chemical and biological processes, yet a fundamental understanding of the ion's hydration environment is a current challenge for experimentalists and theorists alike. In particular, low-frequency internal degrees of freedom make and break hydrogen bonds, providing significant fluctuations to the high-frequency hydrogen-stretch network's local environment. These infrared signatures provide specific fingerprints of the underlying electronic and nuclear rearrangements that must occur throughout the hydration dynamics. Accurately modeling and predicting such dynamics is essential in the development of novel technologies. The challenge arises as a result of significant anharmonicities-including strong vibrational couplings to other degrees of freedom-which give rise to resonant transitions that are difficult to model with traditional anharmonic methodologies. As a result, this research has focused on the development of more advanced theoretical models that are required to describe these systems accurately. The research done in this dissertation is inherently collaborative, and, working together with experimental spectroscopists, we can answer fundamental questions about the mechanism by which strong ions and radicals activate water. These methodologies provide new algorithms for the theoretical community definitively explaining some bizarre vibrational behavior. The research contained in this dissertation is expected to be useful in aiding experimentalists in the development of new efficient catalysts for use in renewable energy technologies, new biotechnologies, and the development of cutting-edge experimental methodologies. |
