Three stages of optimization and simple correlated wave functions
Article first published online: 21 SEP 2004
Copyright © 1994 John Wiley & Sons, Inc.
International Journal of Quantum Chemistry
Volume 49, Issue 1, pages 45–57, 5 January 1994
How to Cite
Hoor, M. J. T. (1994), Three stages of optimization and simple correlated wave functions. Int. J. Quantum Chem., 49: 45–57. doi: 10.1002/qua.560490107
- Issue published online: 21 SEP 2004
- Article first published online: 21 SEP 2004
- Manuscript Accepted: 16 AUG 1993
- Manuscript Revised: 19 JUL 1993
- Manuscript Received: 1 MAR 1993
It is advocated to carry out an optimization procedure, which is based upon the variational method, in such a way that the optimum values of the variational parameters are expressed as functions of physical constants, such as the atomic number, Z. The three stages involved in this treatment are illustrated by the optimization of nine correlated wave functions, which describe the ground states of atomic two-electron systems. An analysis of the Z-expansions of the total energies associated with these functions leads to the concept of a class of variational functions. The performances of functions belonging to the same class differ only marginally, especially at larger values of Z. Consequently, the concept of class may be used to bring some order in the plethora of variational functions. © 1994 John Wiley & Sons, Inc.