Date of Award
Master of Science
Arthur H. Winter
Theoretical and Experimental studies of Oxenium ions
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.
Patrick James Hanway
Hanway, Patrick James, "Theoretical and Experimental Studies of Oxenium Ions" (2012). Graduate Theses and Dissertations. 12612.