Shape-driven graphical unitary group approach to the electron correlation problem. Application to the ethylene molecule
A new method for the approximate solution of Schroedinger's equation for many electron molecular systems is outlined. The new method is based on the unitary group approach (UGA) and exploits in particular the shape of loops appearing in Shavitt's graphical representation for the UGA. The method is cast in the form of a direct CI, makes use of Siegbahn's external space simplifications, and is suitable for very large configuration interaction (CI) wave functions. The ethylene molecule was chosen, as a prototype of unsaturated organic molecules, for the variational study of genuine many (i.e.,>2) body correlation effects. With a double zeta plus polarization basis set, the largest CI included all valence electron single and double excitations with respect to a 703 configuration natural orbital reference function. This variational calculation, involving 1 046 758 spin- and space-adapted /sup 1/A/sub g/ configurations, was carried out on a minicomputer. Triple excitations are found to contribute 2.3% of the correlation energy and quadruple excitations 6.4%.
- Research Organization:
- Department of Chemistry and Lawrence Berkeley Laboratory, University of California, Berkeley, California 94720
- OSTI ID:
- 7062688
- Journal Information:
- J. Chem. Phys.; (United States), Vol. 77:11
- Country of Publication:
- United States
- Language:
- English
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