Descripción: This paper describes a matrix formulation for the correlated hole theory within the framework of the domain-averaged model in many electron systems (atoms, molecules, condensed matter, etc.). General relationships between this quantity and one-particle reduced density matrices for any independent particle or correlated state functions are presented. This formulation turns out to be suitable for computational purposes due to the straightforward introduction of cumulants of two-particle reduced density matrices within the quantum field structure. Numerical calculations in selected simple molecular systems have been performed in order to determine preliminary correlated values for such a quantity.

Descripción: In this paper we propose a functional of the many-body cumulant of the second-order reduced density matrix within the spin-free formalism of quantum chemistry which quantifies the idea of electron correlation and allows one to detect spin entanglement. Its properties are rigorously stated and discussed for spin-adapted pure states. Numerical determinations are performed for both equilibrium conformations and dissociation processes in molecular systems. © 2010 American Institute of Physics.