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Finesse in quantum chemistry: accurate energetics relevant for reaction mechanisms


Carter, Emily Ann (1987) Finesse in quantum chemistry: accurate energetics relevant for reaction mechanisms. Dissertation (Ph.D.), California Institute of Technology.


A general, systematic approach for calculating accurate energetics for chemical processes within the framework of ab initio electronic structure theory is presented. The correlation-consistent configuration interaction (CCCI) method utilizes generalized valence bond wavefunctions as the starting point for the CI, which emphasizes the inclusion of only the dominant correlations dictated by the physics of the problem. The CI expansion truncates quickly, so that processes involving polyatomic molecules, which could not be addressed with conventional CI methodology, may now be treated easily.

A variety of applications of the method are presented, including the prediction of bond energies, electronic excitation energies, and energetics of chemical reactions, for both organic and transition metal-containing molecules. In cases where experimental data are available, the agreement is generally excellent (within 1-5 kcal/mol). We have used these quantitative results, along with qualitative aspects of the wavefunctions, to assess the bonding in and reactivity of a series of organic, organometallic, and inorganic molecules. These studies have produced a number of simple concepts useful for predicting the stability and reactivity of ligands attached to transition metals. Finally, key mechanistic pathways in two transition metal-catalyzed reactions have been examined using the CCCI approach: (i) the chain initiation step for the Fischer-Tropsch synthesis of hydrocarbons; and (ii) the Ag-catalyzed olefin epoxidation reaction.

Item Type:Thesis (Dissertation (Ph.D.))
Degree Grantor:California Institute of Technology
Division:Chemistry and Chemical Engineering
Major Option:Chemistry
Thesis Availability:Public (worldwide access)
Research Advisor(s):
  • Goddard, William A., III
Thesis Committee:
  • Goddard, William A., III (chair)
Defense Date:20 May 1987
Non-Caltech Author Email:eac (AT)
Record Number:CaltechETD:etd-11212003-111159
Persistent URL:
Default Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:4613
Deposited By: Imported from ETD-db
Deposited On:21 Nov 2003
Last Modified:26 Dec 2012 03:10

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PDF (Carter_ea_1987.pdf) - Final Version
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