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As a proof of principle, self-consistent Kohn--Sham calculations are performed with the exact exchange-correlation functional. Finding the exact functional for even one trial density requires solving the interacting Schr\"odinger equation…

化学物理 · 物理学 2014-07-14 Lucas O. Wagner , Thomas E. Baker , E. M. Stoudenmire , Kieron Burke , Steven R. White

Knowledge of exact properties of the exchange-correlation (xc) functional is important for improving the approximations made within density functional theory. Features such as steps in the exact xc potential are known to be necessary for…

强关联电子 · 物理学 2021-01-15 M. J. P. Hodgson , J. D. Ramsden , R. W. Godby

There are several approximations to the exchange-correlation functional in density-functional theory that accurately predict total energy-related properties of many-electron systems, such as binding energies, bond lengths, and crystal…

化学物理 · 物理学 2015-09-30 Eli Kraisler , Tobias Schmidt , Stephan Kümmel , Leeor Kronik

In this chapter, we provide a review of ground-state Kohn-Sham density-functional theory of electronic systems and some of its extensions, we present exact expressions and constraints for the exchange and correlation density functionals,…

化学物理 · 物理学 2022-09-12 Julien Toulouse

We examine the density-functional theory of macroscopic insulators, obtained in the large-cluster limit or under periodic boundary conditions. For polar crystals, we find that the two procedures are not equivalent. In a large-cluster case,…

材料科学 · 物理学 2009-10-28 X. Gonze , Ph. Ghosez , R. W. Godby

Several semilocal exchange potentials usually employed in the framework of density-functional theory (DFT) are tested and compared with their exact counterpart, the exchange Optimized Effective Potential (OEP), as applied to the…

强关联电子 · 物理学 2022-03-14 C. M. Horowitz , C. R. Proetto , J. M. Pitarke

While in principle exact, Kohn-Sham density functional theory -- the workhorse of computational chemistry -- must rely on approximations for the exchange-correlation functional. Despite staggering successes, present-day approximations still…

Most density functionals have been developed by imposing the known exact constraints on the exchange-correlation energy, or by a fit to a set of properties of selected systems, or by both. However, accurate modeling of the conventional…

材料科学 · 物理学 2016-08-24 Jianmin Tao , Yuxiang Mo

The exchange-correlation energy in Kohn-Sham density functional theory can be expressed exactly in terms of the change in the expectation of the electron-electron repulsion operator when, in the many-electron hamiltonian, this same operator…

强关联电子 · 物理学 2009-08-05 Paola Gori-Giorgi , Giovanni Vignale , Michael Seidl

We identify peak and valley structures in the exact exchange-correlation potential of time-dependent density functional theory that are crucial for time-resolved electron scattering in a model one-dimensional system. These structures are…

化学物理 · 物理学 2018-01-03 Yasumitsu Suzuki , Lionel Lacombe , Kazuyuki Watanabe , Neepa T. Maitra

The exchange-correlation hole density of the infinitely stretched (dissociated) hydrogen molecule can be cast into a closed analytical form by using its exact wave function. This permits to obtain an explicit exchange-correlation energy…

化学物理 · 物理学 2017-11-16 Eduard Matito , David Casanova , Xabier Lopez , Jesus M. Ugalde

We review and expand on our work to impose constraints on the effective Kohn Sham (KS) potential of local and semi-local density functional approximations. In this work, we relax a previously imposed positivity constraint, which increased…

Using an end-to-end differentiable implementation of the Kohn-Sham self-consistent field equations, we obtain an accurate neural network-based exchange and correlation (XC) functional of the electronic density. The functional is optimized…

化学物理 · 物理学 2021-06-09 Sebastian Dick , Marivi Fernandez-Serra

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…

Aiming to combine density functional theory (DFT) and wavefunction theory, we study a mapping from the many-body interacting system to an effectively-interacting Kohn-Sham system instead of a non-interacting Kohn-Sham system. Because a…

化学物理 · 物理学 2020-02-19 Shunsuke A. Sato , Angel Rubio

We devise an efficient practical method for computing the Kohn-Sham exchange-correlation potential corresponding to a Hartree-Fock electron density. This potential is almost indistinguishable from the exact-exchange optimized effective…

化学物理 · 物理学 2013-07-09 Ilya G. Ryabinkin , Alexei A. Kananenka , Viktor N. Staroverov

A model is developed, based on the density functional perturbation theory and the inverse Kohn-Sham method, that can be used to improve relativistic nuclear energy density functionals towards an exact but unknown Kohn-Sham…

核理论 · 物理学 2021-04-28 Giacomo Accorto , Tomoya Naito , Haozhao Liang , Tamara Niksic , Dario Vretenar

By extrapolating the energies of non-relativistic atoms and their ions with up to 3000 electrons within Kohn-Sham density functional theory, we find that the ionization potential remains finite and increases across a row, even as…

材料科学 · 物理学 2015-05-19 Lucian A. Constantin , John C. Snyder , John P. Perdew , Kieron Burke

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…

化学物理 · 物理学 2007-05-23 James P. Finley

We discuss energy densities in the strong-interaction limit of density functional theory, deriving an exact expression within the definition (gauge) of the electrostatic potential of the exchange-correlation hole. Exact results for small…

化学物理 · 物理学 2012-11-14 André Mirtschink , Michael Seidl , Paola Gori-Giorgi