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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

The one-particle reduced density matrix functional theory in its natural orbital functional (NOF) version is used to study strongly correlated electrons. We show the ability of the Piris NOF 7 (PNOF7) to describe non-dynamic correlation…

Strongly Correlated Electrons · Physics 2020-02-19 Ion Mitxelena , Mario Piris

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

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

The correct description of nondynamic correlation by electronic structure methods not belonging to the multireference family is a challenging issue. The transition of $D_{2h}$ to $D_{4h}$ symmetry in H$_4$ molecule is among the most simple…

Chemical Physics · Physics 2017-11-16 Eloy Ramos-Cordoba , Xabier Lopez , Mario Piris , Eduard Matito

Occupation numbers of natural orbitals capture the physics of strong electron correlations in momentum space. A Natural Orbital Density Functional Theory based on the antisymmetrized geminal product provides these occupation numbers and the…

Strongly Correlated Electrons · Physics 2014-05-06 B. Barbiellini

The analytic energy gradients with respect to nuclear motion are derived for natural orbital functional (NOF) theory. The resulting equations do not require to resort to linear-response theory, so the computation of NOF energy gradients is…

Chemical Physics · Physics 2017-09-13 Ion Mitxelena , Mario Piris

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

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

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

Natural orbital theory is a computationally useful approach to the few and many-body quantum problem. While natural orbitals are known and applied since many years in electronic structure applications, their potential for time-dependent…

Atomic Physics · Physics 2014-10-08 J. Rapp , M. Brics , D. Bauer

This work assesses the performance of the recently proposed global natural orbital functional (GNOF) against the charge delocalization error. GNOF provides a good balance between static and dynamic electronic correlation leading to accurate…

Chemical Physics · Physics 2023-03-08 Juan Felipe Huan Lew-Yee , Mario Piris , Jorge M. del Campo

We introduce an energy functional for ground-state electronic structure calculations. Its variables are the natural spin-orbitals of singlet many-body wave functions and their joint occupation probabilities deriving from controlled…

Chemical Physics · Physics 2016-12-04 Ralph Gebauer , Morrel H. Cohen , Roberto Car

The exchange-correlation energy in Kohn-Sham density functional theory is expressed as a functional of the electronic density and the Kohn-Sham orbitals. An alternative to Kohn-Sham theory is to express the energy as a functional of the…

Computational Physics · Physics 2009-10-31 S. Goedecker , C. Umrigar

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

We introduce a novel energy functional for ground-state electronic-structure calculations. Its fundamental variables are the natural spin-orbitals of the implied singlet many-body wave function and their joint occupation probabilities. The…

Chemical Physics · Physics 2015-06-23 Ralph Gebauer , Morrel H. Cohen , Roberto Car

Spin-orbit coupling is a single-particle phenomenon known to generate topological order, and electron-electron interactions cause ordered many-body phases to exist. The rich interplay of these two mechanisms is present in a broad range of…

Mesoscale and Nanoscale Physics · Physics 2017-12-20 Weizhe Edward Liu , Stefano Chesi , David Webb , U. Zuelicke , R. Winkler , Robert Joynt , Dimitrie Culcer

Wavefunctions constructed from electron-pair states can accurately model strong electron correlation effects and are promising approaches especially for larger many-body systems. In this article, we analyze the nature and the type of…

Strongly Correlated Electrons · Physics 2016-10-19 Katharina Boguslawski , Paweł Tecmer , Örs Legeza

This chapter provides a comprehensive review of fundamental concepts related to approximate natural orbital functionals (NOFs), emphasizing their significance in quantum chemistry and physics. Focusing on fermions, the discussion excludes…

Chemical Physics · Physics 2023-12-13 Mario Piris

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…

Chemical Physics · Physics 2017-08-16 Mario Piris
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