Defense Date

2022

Document Type

Dissertation

Degree Name

Doctor of Philosophy

Department

Chemistry

First Advisor

M. Samy El-Shall, PhD

Abstract

Investigation of ions-neutral interactions is of fundamental importance to understanding of kinetics and thermodynamics of solution chemistry. While these interactions are challenging to study in the condensed phase given the number of solvent molecules relative to the ion, gas-phase investigation gives control over this ratio allowing the study of each interaction on a stepwise basis. This granular control permits the elucidation of mechanisms and structures in a reaction when paired with thermochemical and DFT calculations. Cumulatively, this allows for the determination of how individual molecules in a series affect the overall structure of an ion-solute interaction and can affect the energetic pathways to attain more stable products.

Given the discovery of benzonitrile in the interstellar medium where it might be subject to ionizing radiation, the need to understand the reactivity of the benzonitrile radical cation has become increasingly salient. To this end, the hydration of the benzonitrile radical cation was investigated. Subsequently the interactions of the benzonitrile radical cation monomer and dimer with methanol were explored. A second ion of interest was the nitrobenzene radical cation which is a commonly used reagent and degradation product of explosives which has similar physical properties to benzonitrile. Reactions of the nitrobenzene radical cation were carried out with water, small alcohols, and nitriles exhibiting a broad range of interesting reactions and solvation behaviors. In each of these projects calculated structures are correlated with thermochemical experimental data to thoroughly describe the reactions and effects of solvation that are observed.

Rights

© The Author

Is Part Of

VCU University Archives

Is Part Of

VCU Theses and Dissertations

Date of Submission

8-3-2022

Available for download on Monday, August 02, 2027

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