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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…

材料科学 · 物理学 2021-09-08 M. J. P. Hodgson

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

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…

A Kohn-Sham density-functional energy expression is derived for any (ground or excited) state within a given many-electron ensemble along with the stationarity condition it fulfills with respect to the ensemble density, thus giving access…

化学物理 · 物理学 2025-01-22 Emmanuel Fromager

The exact static and time-dependent Kohn-Sham (KS) exchange-correlation (xc) potential is extremely challenging to approximate as it is a local multiplicative potential that depends on the electron density everywhere in the system. The KS…

强关联电子 · 物理学 2021-01-15 M. J. P. Hodgson , J. Wetherell

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…

化学物理 · 物理学 2025-04-30 Vaibhav Khanna , Bikash Kanungo , Jeffrey Hatch , Joshua Kammeraad , Paul M. Zimmerman

When a molecule dissociates, the exact Kohn-Sham (KS) and Pauli potentials may form step structures. Reproducing these steps correctly is central for the description of dissociation and charge-transfer processes in density functional theory…

化学物理 · 物理学 2021-03-23 Jakub Kocák , Eli Kraisler , Axel Schild

The reliability of density-functional calculations hinges on accurately approximating the unknown exchange-correlation (xc) potential. Common (semi-)local xc approximations lack the jump experienced by the exact xc potential as the number…

原子物理 · 物理学 2021-01-15 M. J. P. Hodgson , E. Kraisler , E. K. U. Gross

Modern density functional theory (DFT) calculations employ the Kohn-Sham (KS) system of non-interacting electrons as a reference, with all complications buried in the exchange-correlation energy (Exc). The adiabatic connection formula gives…

其他凝聚态物理 · 物理学 2009-10-02 Zhenfei Liu , Kieron Burke

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

Calculating charge transfer (CT) excitation energies with high accuracy and low computational cost is a challenging task. Kohn-Sham density functional theory (KS-DFT), due to its efficiency and accuracy, has achieved great success in…

化学物理 · 物理学 2019-05-01 Yuncai Mei , Weitao Yang

Typical density functional theory (DFT) and approximations thereto solve the many-electron ground state problem by working from a numerically efficient non-interacting Kohn-Sham reference system; and benefit from useful minimization…

化学物理 · 物理学 2025-04-02 Tim Gould

Ground-state Kohn-Sham density functional theory provides, in principle, the exact ground-state energy and electronic spin-densities of real interacting electrons in a static external potential. In practice, the exact density functional for…

化学物理 · 物理学 2022-07-11 Aaron D. Kaplan , Mel Levy , John P. Perdew

Capturing the discontinuous shift by $\Delta$ in the exact exchange-correlation (xc) potential is the standard proposal for calculating the fundamental gap, $E_\mathrm{g}$, from the Kohn-Sham (KS) gap, $\varepsilon_\mathrm{g}$, within KS…

材料科学 · 物理学 2021-01-14 M. J. P. Hodgson , J. Wetherell , Emmanuel Fromager

Standard approximations for the exchange-correlation (XC) functional in Kohn-Sham density functional theory (KS-DFT) typically lead to unacceptably large errors when applied to strongly-correlated electronic systems. Partition-DFT (PDFT) is…

化学物理 · 物理学 2023-09-12 Yi Shi , Yuming Shi , Adam Wasserman

A new method for extracting ensemble Kohn-Sham potentials from accurate excited state densities is applied to a variety of two electron systems, exploring the behavior of exact ensemble density functional theory. The issue of separating the…

We propose exchanging the energy functionals in ground-state DFT with physically equivalent exact force expressions as a new promising route towards approximations to the exchange-correlation potential and energy. In analogy to the usual…

The role of the exchange-correlation potential and the exchange-correlation kernel in the calculation of excitation energues from time-dependent density functional theory is studied. Excitation energies of the He and Be atoms are…

材料科学 · 物理学 2007-05-23 Martin Petersilka , E. K. U. Gross , Kieron Burke

Using the Kohn-Sham (KS) inversion method of Hollins et al. [J. Phys.: Condens. Matter 29, 04LT01 (2017)], we invert densities from variational and diffusion quantum Monte Carlo (QMC) calculations to obtain benchmark QMC-KS potentials for a…

We extend ground-state density-functional theory to excited states and provide the theoretical formulation for the widely used $\Delta SCF$ method for calculating excited-state energies and densities. As the electron density alone is…

化学物理 · 物理学 2024-03-08 Weitao Yang , Paul W. Ayers
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