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Natural orbitals, defined in electronic structure and quantum chemistry as the (molecular) orbitals diagonalizing the one-particle reduced density matrix of the ground state, have been conjectured for decades to be the perfect reference…

Quantum Physics · Physics 2025-09-03 Leonardo Ratini , Chiara Capecci , Leonardo Guidoni

This paper aims at introducing the formal foundations of the application of reduced density-matrix theory and Green's function theory to the analysis of molecular electronic transitions. For this sake, their mechanics, applied to specific…

Chemical Physics · Physics 2022-08-09 Thibaud Etienne

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

The natural and Dyson orbitals are studied for small helium drops comprising 5 to 20 helium atoms interacting via a soft two-body gaussian potential. The wave functions of these drops have been obtained in the hyperspherical cluster model…

Atomic and Molecular Clusters · Physics 2026-05-13 N. K. Timofeyuk

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

We present a novel route to constructing cost-efficient semi-empirical approximations for the non-additive kinetic energy in subsystem density functional theory. The developed methodology is based on the use of Slater determinants composed…

Chemical Physics · Physics 2025-01-13 Larissa Sophie Eitelhuber , Denis G. Artiukhin

In this paper, we investigate the ground state of $N$ bosonic atoms confined in a two-dimensional isotropic harmonic trap, where the atoms interact via a harmonic potential. We derive an exact diagonal representation of the first-order…

Quantum Physics · Physics 2025-02-11 Arkadiusz Kuroś , Adam Pieprzycki , Edyta Gawin , Przemysław Kościk

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 formation and migration energies for various point defects, including vacancies and self-interstitials in aluminum are reinvestigated systematically using the supercell approximation in the framework of orbital-free density functional…

Materials Science · Physics 2020-01-14 Ruizhi Qiu , Haiyan Lu , Bingyun Ao , Li Huang , Tao Tang , Piheng Chen

We investigate the suitability of natural orbitals as a basis for describing many-body excitations. We analyze to which extend the natural orbitals describe both bound as well as ionized excited states and show that depending on the…

Other Condensed Matter · Physics 2011-01-14 N. Helbig , I. V. Tokatly , A. Rubio

The one body density matrix, momentum distribution, natural orbits and quasi hole states of 16O and 40Ca are analyzed in the framework of the correlated basis function theory using state dependent correlations with central and tensor…

Nuclear Theory · Physics 2009-11-06 A. Fabrocini , G. Co'

An exchange-correlation energy functional $ E_{\mathrm xc} $ and the resultant exchange-correlation potential $ v_{\mathrm xc}({\bf r}) $ in density-functional theory are proposed using orbital-dependent coupling-constant-averaged pair…

Strongly Correlated Electrons · Physics 2007-05-23 Hiroshi Yasuhara , Masahiko Higuchi , Yoshiyuki Kawazoe

The exact formulation of multi-configuration density-functional theory (DFT) is discussed in this work. As an alternative to range-separated methods, where electron correlation effects are split in the coordinate space, the combination of…

Chemical Physics · Physics 2015-02-26 Emmanuel Fromager

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

Density functional theory is currently the most widely applied method in electronic structure theory. The Kohn-Sham method, based on a fictitious system of non-interacting particles, is the work horse of the theory. The particular form of…

Chemical Physics · Physics 2016-06-01 Hubertus J J van Dam

Accurate description of deformed atomic nuclei by the orbital-free density functional theory has been a longstanding textbook challenge, due to the difficulty in accounting for the intricate quantum shell effects that are present in such…

Nuclear Theory · Physics 2024-12-31 X. H. Wu , Z. X. Ren , P. W. Zhao

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

The effects of short-range correlations derived from a realistic meson-exchange potential on the single-particle density matrix in finite nuclei are investigated by analyzing the one-body density in terms of the natural orbits. Basic…

Nuclear Theory · Physics 2016-09-08 A. Polls , H. Müther , W. H. Dickhoff

Electron density and electron momentum density, while independently tractable experimentally, bear no direct connection without going through the many-electron wave function. However, invoking a variant of the constrained-search formulation…

Atomic Physics · Physics 2009-11-11 M. K. Harbola , Rajendra R. Zope , Anjali Kshirsagar , Rajeev K. Pathak

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