A tensor product decomposition of the many-electron Hamiltonian

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.

Name thesis:degree_name

Ph. D.

Level thesis:degree_level

doctoral

Discipline thesis:degree_discipline

Physical Chemistry

Department dc:contributor.department

Physical Chemistry

Grantor dc:publisher

Virginia Polytechnic Institute and State University

Year dc:date.issued

1989

Author dc:creator

• Senese, Frederick A.

Chair dc:contributor.committeechair

• Viers, Jimmy W.

Committee members dc:contributor.committeemember

• Schug, John C.
• Graybeal, Jack D.
• Watson, Layne T.
• Beattie, Christopher A.

Statement dc:rights

• In Copyright

Licence dc:rights.uri

• http://rightsstatements.org/vocab/InC/1.0/

Language dc:language.iso

en_US

Handle dc:identifier.uri

http://hdl.handle.net/10919/54413

OAI identifier oai:identifier

oai:vtechworks.lib.vt.edu:10919/54413