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Density functional approximations to the exchange-correlation energy of Kohn-Sham theory, such as the local density approximation and generalized gradient approximations, lack the well-known integer discontinuity, a feature that is critical…

Chemical Physics · Physics 2015-06-18 Martin A. Mosquera , Adam Wasserman

From the perspective of perturbation theory, we propose a systematic procedure for the evaluation of the derivative discontinuity (DD) of the exchange-correlation energy functional in Kohn-Sham density functional theory (KS-DFT), wherein…

Chemical Physics · Physics 2013-01-17 Jeng-Da Chai , Po-Ta Chen

Density functional theory is the workhorse of modern electronic structure calculations, with wide-ranging applications in chemistry, physics, materials science, and machine learning. At its heart lies the exchange-correlation functional, a…

Chemical Physics · Physics 2026-02-20 Fabien Tran , Susi Lehtola , Stefano Pittalis , Miguel A. L. Marques

The derivative discontinuity of the exchange-correlation (xc) energy at integer particle number is a property of the exact, unknown xc functional of density functional theory (DFT) which is absent in many popular local and semilocal…

Strongly Correlated Electrons · Physics 2015-06-11 Gao Xianlong , A-Hai Chen , I. V. Tokatly , S. Kurth

Kohn-Sham density functional theory (DFT) is the workhorse of quantum chemistry, offering an attractive balance between accuracy and computational cost. Although exact in principle, DFT in practice relies on an approximation to the unknown…

Quantum Physics · Physics 2026-05-12 Karim K. Alaa El-Din , Antonius v. Strachwitz , Sam M. Vinko

The derivative discontinuity is a key concept in electronic structure theory in general and density functional theory in particular. The electronic energy of a quantum system exhibits derivative discontinuities with respect to different…

Chemical Physics · Physics 2017-09-13 Paula Mori-Sánchez , Aron J. Cohen

We put forward new approach for the development of a non-local density functional by a direct modeling of the shape of exchange-correlation (xc) hole in inhomogeneous systems. The functional is aimed at giving an accurate xc-energy and an…

Other Condensed Matter · Physics 2013-08-05 Klaas J. H. Giesbertz , Robert van Leeuwen , Ulf von Barth

We formulate diagrammatic rules for many-body perturbation theory which uses Kohn-Sham (KS) Green's functions as basic propagators. The diagram technique allows to study the properties of the dynamic nonlocal exchange-correlation (xc)…

Condensed Matter · Physics 2009-10-31 I. V. Tokatly , O. Pankratov

Specific matrix elements of exchange and correlation kernels in time-dependent density-functional theory are computed. The knowledge of these matrix elements not only constraints approximate time-dependent functionals, but also allows to…

Materials Science · Physics 2009-10-31 X. Gonze , M. Scheffler

Accurately describing excited states within Kohn-Sham (KS) density functional theory (DFT), particularly those which induce ionization and charge transfer, remains a great challenge. Common exchange-correlation (xc) approximations are…

Materials Science · Physics 2021-02-09 Eli Kraisler , M. J. P. Hodgson , E. K. U. Gross

We construct exact Kohn-Sham potentials for the ensemble density-functional theory (EDFT) from the ground and excited states of helium. The exchange-correlation (XC) potential is compared with the quasi-local-density approximation and both…

The exchange-correlation (XC) functional in density functional theory is used to approximate multi-electron interactions. A plethora of different functionals is available, but nearly all are based on the hierarchy of inputs commonly…

A hybrid Kohn-Sham Density Functional Theory (KS-DFT) and 1-electron Reduced Density Matrix Functional Theory (1-RDMFT) has recently been developed to describe strongly correlated systems at mean-field computational cost. This approach…

Computational Physics · Physics 2025-04-14 Daniel Gibney , Jan-Niklas Boyn

Popular approximations to the exchange-correlation (xc) energy of density functional theory do not yield the spatial `step' structures in the exact xc potential which are necessary to describe dissociation and electron excitation with the…

Materials Science · Physics 2021-09-08 M. J. P. Hodgson

Starting from the many-body Bethe-Salpeter equation we derive an exchange-correlation kernel $f_{xc}$ that reproduces excitonic effects in bulk materials within time-dependent density functional theory. The resulting $f_{xc}$ accounts for…

Condensed Matter · Physics 2010-07-01 Lucia Reining , Valerio Olevano , Angel Rubio , Giovanni Onida

Adiabatic time-dependent density functional theory fails for excitations of a heteroatomic molecule composed of two open-shell fragments at large separation. Strong frequency-dependence of the exchange-correlation kernel is necessary for…

Other Condensed Matter · Physics 2009-11-11 Neepa T. Maitra , David G. Tempel

We formulate a rigorous method for calculating a nonadiabatic (frequency-dependent) exchange-correlation (XC) kernel required for correct description of both equilibrium and nonequilibrium properties of strongly correlated systems within…

Strongly Correlated Electrons · Physics 2014-10-13 Volodymyr Turkowski , Talat S. Rahman

Exchange-correlation potentials vxc and energy densities exc are derived for integer and fractional electron counts using an orbital-averaged Kohn-Sham inversion procedure. The reference densities for inversion come from full configuration…

Chemical Physics · Physics 2025-04-30 Vaibhav Khanna , Bikash Kanungo , Jeffrey Hatch , Joshua Kammeraad , Paul M. Zimmerman

One of the most important open challenges in modern Kohn-Sham (KS) density-functional theory (DFT) is the correct treatment of fractional electron charges and spins. Approximate exchange-correlation (XC) functionals struggle to do this in a…

Chemical Physics · Physics 2015-12-24 Jonathan Nafziger , Adam Wasserman

Kohn-Sham (KS) density functional theory (DFT) is a very efficient method for calculating various properties of solids as, for instance, the total energy, the electron density, or the electronic band structure. The KS-DFT method leads to…

Materials Science · Physics 2019-09-20 Fabien Tran , Jan Doumont , Leila Kalantari , Ahmad W. Huran , Miguel A. L. Marques , Peter Blaha