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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

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 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

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

This work combines for the first time ab initio molecular dynamics (AIMD) within the Born-Oppenheimer approximation, with a global natural orbital functional (GNOF), an approximate functional of the one-particle reduced density matrix. The…

Chemical Physics · Physics 2024-01-10 Alejandro Rivero Santamaría , Mario Piris

Recently, an approximate theoretical framework was introduced, called local reduced density matrix functional theory (local-RDMFT), where functionals of the one-body reduced density matrix (1-RDM) are minimized under the additional…

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

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

We showcase the advantages of orbital-free density-potential functional theory (DPFT), a more flexible variant of Hohenberg-Kohn density functional theory. DPFT resolves the usual trouble with the gradient-expanded kinetic energy functional…

Quantum Gases · Physics 2021-06-16 Martin-Isbjörn Trappe , Jun Hao Hue , Berthold-Georg Englert

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

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…

This article presents an overview on recent progress in the theory of nonequilibrium Green functions (NEGF). NEGF, presently, are the only \textit{ab-initio} quantum approach that is able to study the dynamics of correlations for long times…

Strongly Correlated Electrons · Physics 2019-12-20 N. Schluenzen , S. Hermanns , M. Scharnke , M. Bonitz

Density functional theory (DFT) offers a desirable balance between quantitative accuracy and computational efficiency in practical many-electron calculations. Its central component, the exchange-correlation energy functional, has been…

We investigate whether the natural orbitals (NOs) minimize $\lVert\Psi - \Phi\rVert^2$, where $\Psi$ is a wave function and $\Phi$ is a full configuration interaction (CI) approximation to $\Psi$ in a truncated basis. We will show that the…

Quantum Physics · Physics 2013-12-11 Klaas J. H. Giesbertz

The analytic energy gradients in the atomic orbital representation have recently been published (J. Chem. Phys. 146, 014102, 2017) within the framework of the natural orbital functional theory (NOFT). We provide here an alternative…

Chemical Physics · Physics 2018-02-19 Ion Mitxelena , Mario Piris

Due to efficient scaling with electron number N, density functional theory (DFT) is widely used for studies of large molecules and solids. Restriction of an exact mean-field theory to local potential functions has recently been questioned.…

Other Condensed Matter · Physics 2015-06-24 Robert K. Nesbet

New energy-density functionals (EDFs) inspired by effective-field theories (EFTs) have been recently proposed. The present work focuses on three of such functionals which were developed to produce satisfactory equations of state for nuclear…

Nuclear Theory · Physics 2018-09-26 Jérémy Bonnard , Marcella Grasso , Denis Lacroix

We propose a novel scheme to bring reduced density matrix functional theory (RDMFT) into the realm of density functional theory (DFT) that preserves the accurate density functional description at equilibrium, while incorporating accurately…

Chemical Physics · Physics 2014-11-07 Nektarios N. Lathiotakis , Nicole Helbig , Angel Rubio , Nikitas I. Gidopoulos

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

Functionals that explicitly depend on occupied, unoccupied, or fractionally-occupied orbitals are rigorously formalized using Clifford algebras, and a variational principle is established that facilitates orbital (and occupation)…

Quantum Physics · Physics 2024-04-26 Neil Qiang Su
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