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

Abstract

The original formulation (Phys. Rev. Lett. 119, 063002, 2017) of the natural orbital functional - second-order Møller-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.

arXiv comment6 pages, 2 figures, 4 tables

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• The Pauli principle revisited
• Global Method for Electron Correlation
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• Towards a Resolution of the Static Correlation Problem in Density Functional Theory from Semidefinite Programming
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• Electron correlation in the Iron(II) Porphyrin by NOF approximations
• Analytic gradients for spin multiplets in natural orbital functional theory
• $\Delta$NO and the complexities of electron correlation in simple hydrogen clusters
• Performance of the NOF-MP2 method in hydrogen abstraction reactions
• Natural orbital functional for spin-polarized periodic systems
• Orbital-Free Quasi-Density Functional Theory
• Time-Reversal Symmetry in RDMFT and pCCD with Complex-Valued Orbitals
• Resolution of the identity approximation applied to PNOF correlation calculations