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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

Analytic energy gradients with respect to nuclear motion are derived for non-singlet compounds in the natural orbital functional theory. We exploit the formulation for multiplets in order to obtain a simple formula valid for any…

Chemical Physics · Physics 2020-08-26 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 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…

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

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 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

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 computational investigation of photochemical processes often entails the calculation of excited state geometries, energies, and energy gradients. The nuclear-electronic orbital (NEO) approach treats specified nuclei, typically protons,…

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

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 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

Ab initio calculations face the challenge of describing a complex multiscale quantum many-body system. The nuclear wave function has both strong short-range correlations and long-range contributions. Natural orbitals provide a means of…

Nuclear Theory · Physics 2017-04-11 Chrysovalantis Constantinou

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 analytical gradient for periodic systems is presented, for the case of metallic systems. The total energy and the free energy are computed on the Hartree-Fock or density functional level, with the wave function being expanded in terms…

Materials Science · Physics 2012-04-25 K. Doll

Analytic energy gradients are presented for a variational two-electron reduced-density-matrix-driven complete active space self-consistent field (v2RDM-CASSCF) procedure that employs the density-fitting (DF) approximation to the…

Chemical Physics · Physics 2018-11-29 J. Wayne Mullinax , Evgeny Epifanovsky , Gergely Gidofalvi , A. Eugene DePrince

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 molecular electric dipole, quadrupole and octupole moments of a selected set of 21 spin-compensated molecules are determined employing the extended version of the Piris natural orbital functional 6 (PNOF6), using the triple-$\zeta$…

Chemical Physics · Physics 2016-08-11 Ion Mitxelena , Mario Piris

In a recent work, we introduced the foundations of an orthogonally constrained complete active space self-consistent field (OC-CASSCF) framework that produces state-specific molecular orbitals for mutually orthogonal multiconfigurational…

Chemical Physics · Physics 2026-01-28 Loris Delafosse , Vincent Robert , Saad Yalouz

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
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