Determination of Wave Function Functionals: The Constrained-Search--Variational Method

In a recent paper [Phys. Rev. Lett. \textbf{93}, 130401 (2004)], we proposed the idea of expanding the space of variations in variational calculations of the energy by considering the approximate wave function $\psi$ to be a functional of functions $ \chi: \psi = \psi[\chi]$ rather than a function. The space of variations is expanded because a search over the functions $\chi$ can in principle lead to the true wave function. As the space of such variations is large, we proposed the constrained-search-- variational method whereby a constrained search is first performed over all functions $\chi$ such that the wave function functional $\psi[\chi]$ satisfies a physical constraint such as normalization or the Fermi-Coulomb hole sum rule, or leads to the known value of an observable such as the diamagnetic susceptibility, nuclear magnetic constant or Fermi contact term. A rigorous upper bound to the energy is then obtained by application of the variational principle. A key attribute of the method is that the wave function functional is accurate throughout space, in contrast to the standard variational method for which the wave function is accurate only in those regions of space contributing principally to the energy. In this paper we generalize the equations of the method to the determination of arbitrary Hermitian single-particle operators as applied to two-electron atomic and ionic systems. The description is general and applicable to both ground and excited states. A discussion on excited states in conjunction with the theorem of Theophilou is provided.