Theoretical models incorporating electron correlation
Article first published online: 18 JUN 2009
Copyright © 1976 John Wiley & Sons, Inc.
International Journal of Quantum Chemistry
Supplement: Proceedings of the International Symposium on Quantum Biology and Quantum Pharmacology
Volume 10, Issue Supplement S10, pages 1–19, 19/24 January 1976
How to Cite
Pople, J. A., Binkley, J. S. and Seeger, R. (1976), Theoretical models incorporating electron correlation. Int. J. Quantum Chem., 10: 1–19. doi: 10.1002/qua.560100802
- Issue published online: 18 JUN 2009
- Article first published online: 18 JUN 2009
- Manuscript Received: 13 FEB 1976
- National Science Foundation. Grant Number: GP-25617
Some methods of describing electron correlation are compared from the point of view of requirements for theoretical chemical models. The perturbation approach originally introduced by Møller and Plesset, terminated at finite order, is found to satisfy most of these requirements. It is size consistent, that is, applicable to an ensemble of isolated systems in an additive manner. On the other hand, it does not provide an upper bound for the electronic energy. The independent electron-pair approximation is accurate to second order in a Møller-Plesset expansion, but inaccurate in third order. A series of variational methods is discussed which gives upper bounds for the energy, but which lacks size consistency. Finally, calculations on some small molecules using a moderately large Gaussian basis are presented to illustrate these points. Equilibrium geometries, dissociation energies, and energy separations between electronic states of different spin multiplicities are described substantially better by Moller-Plesset theory to second or third order than by Hartree-Fock theory.