From a theoretical standpoint, the accurate description of potential energy surfaces for bond breaking and the equilibrium structures of metal-ligand catalysts are distinctly similar problems. Near degeneracies of the bonding and anti-bonding orbitals for the case of bond breaking and of the partially-filled d-orbitals for the case of metal-ligand catalyst systems lead to strong non-dynamical correlation effects. Standard methods of electronic structure theory, as a consequence of the single-reference approximation, are incapable of accurately describing the electronic structure of these seemingly different theoretical problems. The work within highlights the application of multi-reference methods, methods capable of accurately treating these near-degeneracies, for describing the bond-breaking potentials in several small molecular systems and the equilibrium structures of metal-salen catalysts. The central theme of this work is the ability of small, compact reference functions for accurately describing the strong non-dynamical correlation effects in these systems.
| Identifer | oai:union.ndltd.org:GATECH/oai:smartech.gatech.edu:1853/19807 |
| Date | 14 November 2007 |
| Creators | Sears, John Steven |
| Publisher | Georgia Institute of Technology |
| Source Sets | Georgia Tech Electronic Thesis and Dissertation Archive |
| Detected Language | English |
| Type | Dissertation |
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