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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…

Chemical Physics · Physics 2018-08-22 Mario Piris

The current work presents a natural orbital functional (NOF) for electronic systems with any spin value independent of the external potential being considered, that is, a global NOF (GNOF). It is based on a new two-index reconstruction of…

Chemical Physics · Physics 2021-12-07 Mario Piris

In the past decade, natural orbital functional (NOF) approximations have emerged as prominent tools for characterizing electron correlation. Despite their effectiveness, these approaches, which rely on natural orbitals and their associated…

Chemical Physics · Physics 2024-04-19 Ion Mitxelena , Mario Piris

We present a novel method that appropriately handles both dynamical and static electron correlation in a balanced manner, using a perturbation theory on a spin-extended Hartree-Fock (EHF) wave function reference. While EHF is a suitable…

Strongly Correlated Electrons · Physics 2015-06-22 Takashi Tsuchimochi , Troy Van Voorhis

Multi-configurational approaches yield universal wave function parameterizations that can qualitatively well describe electronic structures along reaction pathways. For quantitative results, multi-reference perturbation theory is required…

Chemical Physics · Physics 2016-09-08 Christopher J. Stein , Vera von Burg , Markus Reiher

The recently proposed natural orbital functional second-order M{\o}ller-Plesset (NOF-MP2) method is capableof achieving both dynamic and static correlation even for those systems with significant multiconfigurational character. We test its…

Chemical Physics · Physics 2019-06-12 Xabier Lopez , Mario Piris

Natural orbital functional (NOF) theory offers a promising approach for studying strongly correlated systems at an affordable computational cost, with an accuracy comparable to highly demanding wavefunction-based methods. However, its…

Strongly Correlated Electrons · Physics 2025-01-31 Juan Felipe Huan Lew-Yee , Jorge M. del Campo , Mario Piris

The relative stability of the singlet, triplet, and quintet spin states of Iron(II) porphyrin (FeP) represents a challenging problem for electronic structure methods. While it is currently accepted that the ground state is a triplet,…

Chemical Physics · Physics 2023-01-05 Juan Felipe Huan Lew-Yee , Jorge M. del Campo , Mario Piris

The account of electron correlation and its efficient separation into dynamic and nondynamic parts plays a key role in the development of computational methods. In this paper we suggest a physically-sound matrix formulation to split…

Chemical Physics · Physics 2016-08-16 Eloy Ramos-Cordoba , Pedro Salvador , Eduard Matito

Electron correlations in molecules can be divided in short range dynamical correlations, long range Van der Waals type interactions and near degeneracy static correlations. In this work we analyze for a one-dimensional model of a…

Chemical Physics · Physics 2014-05-13 K. J. H. Giesbertz , R. van Leeuwen

The $\Delta \text{NO}$ method for static correlation is combined with second-order M{\o}ller-Plesset perturbation theory (MP2) and coupled-cluster singles and doubles (CCSD) to account for dynamic correlation. The MP2 and CCSD expressions…

Chemical Physics · Physics 2020-06-05 Joshua W. Hollett , Pierre-François Loos

Some of the most spectacular failures of density-functional and Hartree-Fock theories are related to an incorrect description of the so-called static electron correlation. Motivated by recent progress on the N-representability problem of…

New ways to treat electron correlation in electronic structure problems are discussed in the context of many-electron theory. The present work focuses primarily on static correlation. In related work, a method for including dynamical…

Chemical Physics · Physics 2018-09-05 Jerry L. Whitten

The natural orbital functional theory (NOFT) has emerged as an alternative formalism to both density functional (DF) and wavefunction methods. In NOFT, the electronic structure is described in terms of the natural orbitals (NOs) and their…

Computational Physics · Physics 2020-10-28 Mario Piris , Ion Mitxelena

A new method to determine electron correlation energy is described. This method is based on a better representation of the potential due to interacting electrons that is obtained by specifying both the average and standard deviation. The…

Materials Science · Physics 2007-05-23 T. R. S. Prasanna

A natural orbital functional for electronic systems with any value of the spin is proposed. This energy functional is based on a new reconstruction for the two-particle reduced density matrix (2RDM) of the multiplet, that is, of the mixed…

Chemical Physics · Physics 2019-10-02 Mario Piris

The Global Natural Orbital Functional (GNOF) provides a straightforward approach to capture most electron correlation effects without needing perturbative corrections or limited active spaces selection. In this work, we evaluate both the…

Chemical Physics · Physics 2026-02-10 Ion Mitxelena , Juan Felipe Huan Lew-Yee , Mario Piris

The $\Delta$NO two-electron density matrix (2-RDM) and energy expression are derived from a multideterminantal wave function. The approximate $\Delta$NO 2-RDM is combined with an on-top density functional and a double-counting correction to…

Chemical Physics · Physics 2022-03-14 Ismael A. Elayan , Rishabh Gupta , Joshua W. Hollett

Favorably scaling numerical time-dependent many-electron techniques such as time-dependent density functional theory (TDDFT) with adiabatic exchange-correlation potentials typically fail in capturing highly correlated electron dynamics. We…

Atomic Physics · Physics 2013-11-25 M. Brics , D. Bauer

Natural orbital functional theory is considered for systems with one or more unpaired electrons. An extension of the Piris natural orbital functional (PNOF) based on electron pairing approach is presented, specifically, we extend the…

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