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Rule-Based Trial Wave Functions for Generalized Valence Bond Theory

Langlois, Jean-Marc and Yamasaki, Terumasa and Muller, Richard P. and Goddard, William A., III (1994) Rule-Based Trial Wave Functions for Generalized Valence Bond Theory. Journal of Physical Chemistry, 98 (51). pp. 13498-13505. ISSN 0022-3654.

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We present a general method suitable for automatic generation of trial wave functions for generalized valence bond (GVB) descriptions of large molecules. This method uses pseudo-Hartree-Fock (P-HF) molecular orbitals formed from HF atomic orbitals but without Fock matrix diagonalization. The occupied P-HF orbitals are projected onto atomic basis functions to obtain GVB first natural orbitals, and the unoccupied HF orbitals are projected to obtain GVB second natural orbitals. This method (denoted GVB-INIT) is fast because no HF wave functions need be calculated and because the localization is piecewise atomic. In conjunction with the recently developed GVB-DIIS method for converging GVB wave functions and the new pseudospectral programs (PS-GVB) for the Fock matrix elements, GVB-INIT makes calculation of highly correlated GVB wave functions quite practical. The efficacy of GVB-INIT is illustrated by application to several cases including GVB wave functions with up to 26 correlated pairs.

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Goddard, William A., III0000-0003-0097-5716
Additional Information:© 1994 American Chemical Society. Received: June 20, 1994; In Final Form: October 4, 1994. This research was partially funded by the National Science Foundation (Che 91-100284 and ASC 92-17368). The facilities at the MSC/BI are also supported by grants from DOE-AICD, Allied-Signal Corp., Asahi Chemical, Asahi Glass, BP America, Chevron Petroleum Technology Co., B.F. Goodrich, Teijin Ltd., Hughes Research Labs., Xerox Corp., and Beckman Institute. Some of these calculations were carried out on the NSF Pittsburgh Supercomputing Center and some on the JPL Cray YMP.
Funding AgencyGrant Number
NSFCHE 91-100284
NSFASC 92-17368
Department of Energy (DOE)UNSPECIFIED
Allied-Signal Corp.UNSPECIFIED
Chevron Petroleum Technology Co.UNSPECIFIED
Hughes Research LaboratoriesUNSPECIFIED
Caltech Beckman InstituteUNSPECIFIED
Issue or Number:51
Record Number:CaltechAUTHORS:20180313-103941664
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Official Citation:Rule-Based Trial Wave Functions for Generalized Valence Bond Theory. Jean-Marc Langlois, Terumasa Yamasaki, Richard P. Muller, and William A. III Goddard. The Journal of Physical Chemistry 1994 98 (51), 13498-13505 DOI: 10.1021/j100102a012
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:85276
Deposited By: Tony Diaz
Deposited On:13 Mar 2018 17:55
Last Modified:03 Oct 2019 19:29

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