Degree Type

Thesis

Date of Award

2012

Degree Name

Master of Science

Department

Chemistry

First Advisor

Arthur H. Winter

Abstract

Theoretical and Experimental studies of Oxenium ions

Patrick Hanway

Iowa State University

The geometries and energies of the phenyloxenium ion were computed at the CASSCF/CASPT2 multireference level of theory. The 1A1 was shown to be the ground state being 22 kcal/mol lower in energy than the 3A2 (n to p*) state. It was found that electron-withdrawing groups in the para position slightly stabilize the singlet compared to the triplet and electron-donating groups have the opposite effect. Electron-donating groups (NH2) in the meta position lead to nearly degenerate singlet triplet states. All the product studies suggest the formation of the phenyloxenium ion. The geometries and energies of heteroaryl oxenium ions were also computed using CASSCF/CASPT2. These results show that the 2- and 3-pyridyl oxenium ions have energies and states that are similar to the phenyloxenium ion. The 4-pyridyl, pyrimidinyl, and pyrizidinyl oxenium ions however have very different energetics from the phenyloxenium ion.

DOI

https://doi.org/10.31274/etd-180810-3086

Copyright Owner

Patrick James Hanway

Language

en

File Format

application/pdf

File Size

53 pages

Appendices.pdf (9041 kB)
Appendices

Included in

Chemistry Commons

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