The dynamic electron-correlation energy in the NOF-MP2 method from the orbital-invariant perturbation theory

TL;DR

This paper reformulates the NOF-MP2 method using orbital-invariant MP2 to better capture dynamic and static correlations, improving energy calculations and dissociation behavior in molecules.

Contribution

It introduces an orbital-invariant formulation of NOF-MP2 and modifies the natural orbital functional to enhance correlation treatment and dissociation accuracy.

Findings

Improved total and relative energies in polyatomic molecules.

Proper dissociation of noble gas dimers.

Enhanced description of static and dynamic correlations.

Abstract

The original formulation (Phys. Rev. Lett. 119, 063002, 2017) of the natural orbital functional - second-order M{\o}ller-Plesset (NOF-MP2) method is based on the MP2 that uses the canonical Hartree-Fock molecular orbitals. The current work presents a reformulation of the dynamic energy correction based on the orbital-invariant MP2, which allows to attain both dynamic and static correlations even for those systems with strong orbital localizability and significant multiconfigurational character. To improve the reference Slater determinant formed with natural orbitals, the natural orbital functional that generates them is also modified to take into account only the inter-pair static correction. This more general NOF-MP2 is able to dissociate properly noble gas dimers, which remain as non-bound species within the canonical formulation. Test calculations in a selected set of 30 polyatomic molecules demonstrate a substantial improvement not only of the relative energies but also of the total energies calculated with the NOF-MP2 method.