A new direct full variational approach is described. The approach exploits a tensor (Kronecker) product construction of the many-electron Hamiltonian and has a number of computational advantages. Explicit assembly and storage of the Hamiltonian matrix is avoided by using the Kronecker product structure to form matrix-vector products directly from the molecular integrals. Computation-intensive integral transformations and formula tapes are unnecessary. The wavefunction is expanded in terms of spin-free primitive kets rather than Slater determinants or configuration state functions and is equivalent to a full configuration interaction expansion. The approach suggests compact storage schemes and algorithms which are naturally suited to parallel and pipelined machines.
Sample calculations for small two- and four-electron systems are presented. The preliminary ground state potential energy surface of the hydrogen molecule dimer is computed by the tensor product method using a small basis set. / Ph. D.
| Identifer | oai:union.ndltd.org:VTETD/oai:vtechworks.lib.vt.edu:10919/54413 |
| Date | January 1989 |
| Creators | Senese, Frederick A. |
| Contributors | Physical Chemistry, Viers, Jimmy W., Schug, John C., Graybeal, Jack D., Watson, Layne T., Beattie, Christopher A. |
| Publisher | Virginia Polytechnic Institute and State University |
| Source Sets | Virginia Tech Theses and Dissertation |
| Language | en_US |
| Detected Language | English |
| Type | Dissertation, Text |
| Format | viii, 137 leaves, application/pdf, application/pdf |
| Rights | In Copyright, http://rightsstatements.org/vocab/InC/1.0/ |
| Relation | OCLC# 20112333 |
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