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We establish necessary and sufficient conditions for the N-representability of the universal one-electron reduced density matrix functional. Functionals satisfying these conditions are guaranteed to yield variational upper bounds on the…

Quantum Physics · Physics 2026-04-08 Jannis Erhard , Paul W. Ayers

Self-interaction is a fundamental flaw of practical Kohn-Sham Density Functional Theory (KS DFT) approximations responsible for numerous qualitative and even catastrophic shortcomings. Whereas self-interaction is easy to characterize in…

Chemical Physics · Physics 2024-07-16 Samuel A. Slattery , Edward F. Valeev

We introduce new and robust decompositions of mean-field Hartree-Fock (HF) and Kohn-Sham density functional theory (KS-DFT) relying on the use of localized molecular orbitals and physically sound charge population protocols. The new…

Chemical Physics · Physics 2020-12-04 Janus J. Eriksen

A mathematical framework for reduced density matrix functional theory (RDMFT) is proposed. The work is inspired by and generalizes the work by E.H.~Lieb [E.H. Lieb, Int. J. Quant. Chem. 24(1983), pp.243--277] on density-functional theory…

Mathematical Physics · Physics 2026-01-06 Håkon R. Fredheim , Simen Kvaal

Reduced density-matrix functional theory (RDMFT) has become an appealing alternative to density-functional theory to describe electronic properties of highly-correlated systems. Here we derive exact conditions for the suitability of RDMFT…

Strongly Correlated Electrons · Physics 2012-04-19 A. Putaja , E. Rasanen

We develop a systematic approach to construct energy functionals of the one-particle reduced density matrix (1RDM) for equilibrium systems at finite temperature. The starting point of our formulation is the grand potential $\Omega…

Other Condensed Matter · Physics 2018-11-20 Klaas J. H. Giesbertz , Anna-Maija Uimonen , Robert van Leeuwen

Recently a novel approach to find approximate exchange-correlation functionals in density-functional theory (DFT) was presented (U. Mordovina et. al., JCTC 15, 5209 (2019)), which relies on approximations to the interacting wave function…

Chemical Physics · Physics 2021-03-04 Iris Theophilou , Teresa E. Reinhard , Angel Rubio , Michael Ruggenthaler

In this review we provide a rigorous and self-contained presentation of one-body reduced density-matrix (1RDM) functional theory. We do so for the case of a finite basis set, where density-functional theory (DFT) implicitly becomes a 1RDM…

Mathematical Physics · Physics 2019-06-07 Klaas J. H. Giesbertz , Michael Ruggenthaler

In this work we get insight into the impact of reduced density matrix functionals on the quality of removal/addition energies obtained using the Extended Koopmans' Theorem (EKT). Within reduced density matrix functional theory (RDMFT) the…

Strongly Correlated Electrons · Physics 2022-12-26 S. Di Sabatino , J. Koskelo , J. A. Berger , P. Romaniello

A generalization of the Kohn--Sham approach is derived where the correlation-energy functional depends on the one-particle density matrix of noninteracting states and on the external potential from the interacting target-state. The…

Chemical Physics · Physics 2007-05-23 James P. Finley

A density functional theory (DFT) of lattice fermion models is presented, which uses the single-particle density matrix gamma_{ij} as basic variable. A simple, explicit approximation to the interaction-energy functional W[gamma] of the…

Strongly Correlated Electrons · Physics 2009-11-07 R. Lopez-Sandoval , G. M. Pastor

The exponential computational cost of describing strongly correlated electrons can be mitigated by adopting a reduced density-matrix (RDM)-based description of the electronic structure. While variational two-electron RDM (v2RDM) methods can…

Chemical Physics · Physics 2026-01-06 Grier M. Jones , Run. R. Li , A. Eugene DePrince , Konstantinos D. Vogiatzis

We develop an energy density matrix that parallels the one-body reduced density matrix (1RDM) for many-body quantum systems. Just as the density matrix gives access to the number density and occupation numbers, the energy density matrix…

Strongly Correlated Electrons · Physics 2015-06-22 Jaron T. Krogel , Jeongnim Kim , Fernando A. Reboredo

We introduce 'single-particle-exact density functional theory' (1pEx-DFT), a novel density functional approach that represents all single-particle contributions to the energy with exact functionals. Here, we parameterize interaction energy…

General theorem describing a relation between diagonal of one-electron density matrix and a certain class of many-electron ensembles of determinant states is proved. As a corollary to this theorem a constructive proof of sufficiency of…

Chemical Physics · Physics 2007-05-23 A. I. Panin , A. N. Petrov

In approximate Kohn-Sham density-functional theory, self-interaction manifests itself as the dependence of the energy of an orbital on its fractional occupation. This unphysical behavior translates into qualitative and quantitative errors…

Materials Science · Physics 2010-09-28 Ismaila Dabo , Andrea Ferretti , Nicolas Poilvert , Yanli Li , Nicola Marzari , Matteo Cococcioni

Reduced density-matrix functional theory (RDMFT) is a promising alternative approach to the problem of electron correlation. Like standard density functional theory, it contains an unknown exchange-correlation functional, for which several…

Chemical Physics · Physics 2017-03-03 N. N. Lathiotakis , Miguel A. L. Marques

We present a rigorous formulation of generalized Kohn-Sham density-functional theory. This provides a straightforward Kohn-Sham description of many-body systems based not only on particle-density but also on any other observable. We…

Strongly Correlated Electrons · Physics 2008-02-03 M. Valiev , G. W. Fernando

In many of the approximate functionals in one-body reduced density matrix (1RDM) functional theory, the approximate two-body reduced density matrix (2RDM) in the natural orbital representation only depends on the natural occupation numbers.…

Chemical Physics · Physics 2020-11-24 Klaas J. H. Giesbertz

We use projector operators to correct the Kohn-Sham Hamiltonian of density functional theory (KS-DFT) so that the resulting mean-field scheme yields, in finite systems, virtual orbitals and energy gaps in better agreement with those…

Other Condensed Matter · Physics 2008-06-26 Hector Mera