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By exploiting freedoms in the definitions of 'correlation', 'exchange' and 'Hartree' physics in ensemble systems we better generalise the notion of 'exact exchange' (EXX) to systems with fractional occupations functions of the frontier…

Atomic Physics · Physics 2014-07-28 Tim Gould , John F. Dobson

Most approximate exchange-correlation functionals used within density functional theory are constructed as the sum of two distinct contributions for exchange and correlation. Separating the exchange component from the entire functional is…

Condensed Matter · Physics 2009-10-28 Claudia Filippi , C. J. Umrigar , Xavier Gonze

We consider two perturbative schemes to calculate excitation energies, each employing the Kohn-Sham Hamiltonian as the unperturbed system. Using accurate exchange-correlation potentials generated from essentially exact densities and their…

Condensed Matter · Physics 2009-10-30 Claudia Filippi , C. J. Umrigar , X. Gonze

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

Following a recent work [E. Fromager, J. Phys. Chem. A 2025, 129, 4, 1143-1155] on the ensemble density functional theory (DFT) of excited electronic energy levels, we derive in this paper the ensuing static linear response theory, thus…

Chemical Physics · Physics 2025-09-26 Lucien Dupuy , Emmanuel Fromager

The exact-exchange relativistic density functional theory (Ex-RDFT) of atomic nuclei has been solved in three-dimensional lattice space for the first time. The exchange energy is treated within the framework of the orbital-dependent…

Nuclear Theory · Physics 2024-12-16 Qiang Zhao , Zhengxue Ren , Pengwei Zhao , Kenichi Yoshida

Spin is a fundamental property of any many-electron system. The ability of density functional theory to accurately predict the physical properties of a system, while varying its spin, is crucial for describing magnetic materials and…

Chemical Physics · Physics 2024-11-05 Alon Hayman , Eli Kraisler , Tamar Stein

The spin-dependent localized Hartree-Fock (SLHF) density-functional approach is extended to the treatment of the inner-shell excited-state calculation of open-shell atomic systems. In this approach, the electron spin-orbitals in an…

Atomic Physics · Physics 2009-11-13 Zhongyuan Zhou , Shih-I Chu

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…

Materials Science · Physics 2007-05-23 Martin Petersilka , E. K. U. Gross , Kieron Burke

A recently developed quasi two-dimensional exact-exchange formalism within the framework of Density Functional Theory has been applied to a strongly inhomogeneous interacting electron gas, and the results were compared with state-of-the-art…

Condensed Matter · Physics 2009-11-07 S. Rigamonti , F. A. Reboredo , C. R. Proetto

We report on a methodology for the treatment of the Coulomb energy and potential in Kohn-Sham density functional theory that is free from self-interaction effects. Specifically, we determine the Coulomb potential given as the functional…

Materials Science · Physics 2016-06-29 M. Däne , A. Gonis , D. M. Nicholson , G. M. Stocks

Early work extending the Kohn-Sham theory to excited states utilized an ensemble average of the Hamiltonian considered as a functional of the corresponding average density. We propose and develop an alternative that utilizes the matrix…

Atomic Physics · Physics 2007-05-23 Abraham Klein , Reiner M. Dreizler

An exchange energy functional is proposed and tested for obtaining a class of excited-state energies using density-functional formalism. The functional is the excited-state counterpart of the local-density approximation functional for the…

Other Condensed Matter · Physics 2007-05-23 Prasanjit Samal , Manoj K. Harbola

The State--Specific Kohn--Sham Density Functional Theory [arXiv:physics/0506037] is used to derive the Kohn-Sham exchange-correlation potential $\vxc$ and exchange-correlation energy $\Eco$ as explicit functionals of $v_s$ and $\phi_1$,…

Chemical Physics · Physics 2025-01-31 James P. Finley

Density functional theory has been an essential analysis tool for both theoretical and experimental chemists since accurate hybrid functionals were developed. Here we propose a local hybrid method derived from the optimized effective…

Chemical Physics · Physics 2017-03-24 Jaewook Kim , Kwangwoo Hong , Sang-Yeon Hwang , Seongok Ryu , Sunghwan Choi , Woo Youn Kim

Ensemble density functional theory (EDFT) is a promising alternative to time-dependent density functional theory for computing electronic excitation energies. Using coordinate scaling, we prove several fundamental exact conditions in EDFT…

Strongly Correlated Electrons · Physics 2023-07-04 Thais R. Scott , John Kozlowski , Steven Crisostomo , Aurora Pribram-Jones , Kieron Burke

Ground and excited states of a confined negative Hydrogen ion has been pursued under Kohn-Sham density functional approach by invoking a physically motivated work-function-based exchange potential. The exchange-only results are of near…

Atomic Physics · Physics 2022-05-23 Sangita Majumdar , Neetik Mukherjee , Amlan K. Roy

Gross-Oliveira-Kohn density-functional theory (GOK-DFT) for ensembles is the DFT analog of state-averaged wavefunction-based (SA-WF) methods. In GOK-DFT, the state-averaged (so-called ensemble) exchange-correlation (xc) energy is described…

Chemical Physics · Physics 2019-03-07 Killian Deur , Emmanuel Fromager

In order to assess the accuracy of commonly used approximate exchange-correlation density functionals, we present a comparison of accurate exchange and correlation potentials, exchange energy densities and energy components with the…

Condensed Matter · Physics 2007-05-23 Claudia Filippi , Xavier Gonze , C. J. Umrigar

This work merges two different types of many-electron ensembles, namely the Theophilou-Gross-Oliveira-Kohn ensembles of ground and neutrally-excited states, and the more recent $N$-centered ensembles of neutral and charged ground states. On…

Chemical Physics · Physics 2024-06-10 Filip Cernatic , Pierre-François Loos , Bruno Senjean , Emmanuel Fromager