Dissertations, Theses, and Capstone Projects

Date of Degree

10-2014

Document Type

Dissertation

Degree Name

Ph.D.

Program

Chemistry

Advisor

Louis J. Massa

Subject Categories

Chemistry | Computer Sciences | Other Physics

Keywords

Acidic Solvents, Hydronium Cations, Quantum Crystallography, Water Clusters

Abstract

Cationic hydronium clusters of the form [HaOb]^c,(c>0), have been investigated. After investigating over 2000 crystal structures containing hydronium cations found in the Cambridge Structural Database. The hydronium cationic compounds that were most unusual, mischaracterized, or those of apparent aggregates, were investigated further by geometry optimization and in some cases with the Quantum Theory of Atoms in Molecules (QTAIM). The results of our investigations yielded the first reports of stable conformations of cyclic dihydronium cationic clusters. In a second investigation we reported the first theoretically confirmed transition state of a H7O3+conformer captured within a crystal. A third product from our efforts was the theoretically viable, cubic arrangement of 3[H3O+]3[H2O]2[OH-] derived from the observed behavior of hydronium cationic clusters.

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