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We show that using complex, spin-restricted orbitals (cR) in Kohn-Sham density functional theory (KS-DFT) allows one to access a new class of densities that is not accessible by either spin-restricted (RKS) or spin-unrestricted (UKS)…

Chemical Physics · Physics 2019-09-13 Joonho Lee , Luke W. Bertels , Martin Head-Gordon

Perdew et al. [Phys. Rev. Lett 49, 1691 (1982)] discovered and proved two different properties of exact Kohn-Sham density functional theory (DFT): (i) The exact total energy versus particle number is a series of linear segments between…

Other Condensed Matter · Physics 2015-03-13 Tamar Stein , Jochen Autschbach , Niranjan Govind , Leeor Kronik , Roi Baer

The dissociation of molecules, even the most simple hydrogen molecule, cannot be described accurately within density functional theory because none of the currently available functionals accounts for strong on-site correlation. This problem…

Strongly Correlated Electrons · Physics 2011-01-14 N. Helbig , I. V. Tokatly , A. Rubio

We present a kinetic-energy density-functional theory and the corresponding kinetic-energy Kohn-Sham (keKS) scheme on a lattice and show that by including more observables explicitly in a density-functional approach already simple…

Chemical Physics · Physics 2018-07-23 Iris Theophilou , Florian Buchholz , F. G. Eich , Michael Ruggenthaler , Angel Rubio

Informed by an abstraction of Kohn-Sham computation called a KS machine, a functional analytic perspective is developed on mathematical aspects of density functional theory. A natural semantics for the machine is bivariate, consisting of a…

Other Condensed Matter · Physics 2023-09-25 Paul E. Lammert

The relationship between the exact kinetic energy density in a quantum system in the frame of Density Functional Theory and the semiclassical functional expression for the same quantity is investigated. The analysis is performed with Monte…

Atomic and Molecular Clusters · Physics 2014-12-15 D. I. Palade

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…

Strongly Correlated Electrons · Physics 2021-01-15 M. J. P. Hodgson , J. Wetherell

It is known that the asymptotic decay of the electron density $n(\br)$ outside a molecule is informative about its first ionization potential $I_0$, $n(|\br|\to\infty) \sim \text{exp}(-2\sqrt{2I_0}\,r)$. This dictates the orbital energy of…

Chemical Physics · Physics 2015-12-31 P. Gori-Giorgi , T. Gál , E. J. Baerends

The conventional approaches to the inverse density functional theory problem typically assume non-degeneracy of the Kohn-Sham (KS) eigenvalues, greatly hindering their use in open-shell systems. We present a generalization of the inverse…

Chemical Physics · Physics 2024-01-09 Bikash Kanungo , Jeffrey Hatch , Paul M. Zimmerman , Vikram Gavini

A relativistic density-functional theory based on a Fock-space effective quantum-electrodynamics (QED) Hamiltonian using the Coulomb or Coulomb-Breit two-particle interaction is developed. This effective QED theory properly includes the…

Chemical Physics · Physics 2021-05-03 Julien Toulouse

We formulate the Kohn-Sham density functional theory (KS-DFT) as a statistical theory in which the electron density is deter-mined from an average of correlated stochastic densities in a trace formula. The key idea is that it is sufficient…

Materials Science · Physics 2015-06-15 Roi Baer , Daniel Neuhauser , Eran Rabani

A bivariate perspective on Kohn-Sham density functional theory is proposed, treating potential and density as simultaneous independent variables, and used to make fruitful connection between Lieb's rigorous foundational framework and…

Materials Science · Physics 2020-07-07 Paul E. Lammert

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 use the exact strong-interaction limit of the Hohenberg-Kohn energy density functional to construct an approximation for the exchange-correlation term of the Kohn-Sham approach. The resulting exchange-correlation potential is able to…

Strongly Correlated Electrons · Physics 2013-04-05 Francesc Malet , André Mirtschink , Jonas C. Cremon , Stephanie M. Reimann , Paola Gori-Giorgi

Development of the electronic kinetic-energy density functional is a subject of major interest in theoretical physics and chemistry. In this work, the nonlocal kinetic-energy functional is developed in terms of the response function for the…

Chemical Physics · Physics 2022-06-17 Hideaki Takahashi

Simulations in the warm dense matter regime using finite temperature Kohn-Sham density functional theory (FT-KS-DFT), while frequently used, are computationally expensive due to the partial occupation of a very large number of high-energy…

Materials Science · Physics 2018-04-04 Yael Cytter , Eran Rabani , Daniel Neuhauser , Roi Baer

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,…

Chemical Physics · Physics 2022-09-12 Julien Toulouse

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…

Materials Science · Physics 2015-05-19 Lucian A. Constantin , John C. Snyder , John P. Perdew , Kieron Burke

We re-adapt a spectral renormalization method, introduced in nonlinear optics, to solve the Kohn-Sham (KS) equations of density functional theory (DFT), with a focus on functionals based on the strictly-correlated electrons (SCE) regime,…

Strongly Correlated Electrons · Physics 2020-04-23 Juri Grossi , Ziad H. Musslimani , Michael Seidl , Paola Gori-Giorgi

Exact density functionals for the exchange and correlation energies are approximated in practical calculations for the ground-state electronic structure of a many-electron system. An important exact constraint for the construction of…