This work was presented by R. J. Bartlett as part of an invited presentation at the American Theoretical Chemistry Conference, Boulder, Colorado, 1978.
Many-body perturbation theory, coupled-pair many-electron theory, and the importance of quadruple excitations for the correlation problem†
Article first published online: 19 OCT 2004
Copyright © 1978 John Wiley & Sons, Inc.
International Journal of Quantum Chemistry
Volume 14, Issue 5, pages 561–581, November 1978
How to Cite
Bartlett, R. J. and Purvis, G. D. (1978), Many-body perturbation theory, coupled-pair many-electron theory, and the importance of quadruple excitations for the correlation problem. Int. J. Quantum Chem., 14: 561–581. doi: 10.1002/qua.560140504
- Issue published online: 19 OCT 2004
- Article first published online: 19 OCT 2004
- Manuscript Accepted: 1 AUG 1978
- Manuscript Revised: 31 JUL 1978
- Manuscript Received: 17 JUL 1978
Many-body (diagrammatic) perturbation theory (MBPT), coupled-pair many-electron theory (CPMET), and configuration interaction (CI) are investigated with particular emphasis on the importance of quadruple excitations in correlation theories. These different methods are used to obtain single, double, and quadruple excitation contributions to the correlation energy for a series of molecules including CO2, HCN, N2, CO, BH3, and NH3. It is demonstrated that the sum of double and quadruple excitation diagrams through fourth-order perturbation theory is usually quite close to the CPMET result for these molecules at equilibrium geometries. The superior reliability of the CPMET model as a function of internuclear separation is illustrated by studying the 1∑ potential curve of Be2. This molecule violates the assumption common to nondegenerate perturbation theory that only a single reference function is important and this causes improper behavior of the potential curve as a function of R. This is resolved once the quadruple excitation terms are fully included by CPMET.