Global Method for Electron Correlation

TL;DR

This paper introduces a novel single-reference method combining static and dynamic electron correlation effects using natural orbitals and energy functionals, achieving accurate results for molecular dissociation.

Contribution

A new method called NOF-MP2 that unifies static and dynamic correlation treatments with size-consistency and good experimental agreement.

Findings

Successfully applied to diatomic molecule dissociation

Achieves good agreement with experimental data

Scales as O(M^5) with basis functions

Abstract

The current work presents a new single-reference method for capturing at the same time the static and dynamic electron correlation. The starting-point is a determinant wavefunction formed with natural orbitals obtained from a new interacting-pair model. The latter leads to a natural orbital functional (NOF) capable of recovering the complete intra-pair, but only the static inter-pair correlation. Using the solution of the NOF, two new energy functionals are defined for both dynamic (Edyn) and static (Esta) correlation. Edyn is derived from a modified second-order Moller-Plesset perturbation theory (MP2), while Esta is obtained from the static component of the new NOF. Double counting is avoided by introducing the amount of static and dynamic correlation in each orbital as a function of its occupation. As a result, the total energy is represented by the sum Ehf + Edyn + Esta, where Ehf is the Hartree-Fock energy obtained with natural orbitals. The new procedure called NOF-MP2 scales formally as O(M^5)(M: number of basis functions), and is applied successfully to the homolytic dissociation of a selected set of diatomic molecules, paradigmatic cases of near-degeneracy effects. Its size-consistency has been numerically demonstrated for singlets. The values obtained are in good agreement with the experimental data.