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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 propose a practical approximation to the exchange-correlation functional of (time-dependent) density functional theory for many-electron systems coupled to photons. The (time non-local) optimized effective potential (OEP) equation for…

Mesoscale and Nanoscale Physics · Physics 2015-09-02 Camilla Pellegrini , Johannes Flick , Ilya V. Tokatly , Heiko Appel , Angel Rubio

Kohn-Sham inversion, that is, the finding of the exact Kohn-Sham potential for a given density, is difficult in localized basis sets. We study the precision and reliability of several inversion schemes, finding estimates of density-driven…

Chemical Physics · Physics 2020-04-27 Seungsoo Nam , Suhwan Song , Eunji Sim , Kieron Burke

The asymmetric Hubbard dimer is a model that allows for explicit expressions of the Hartree-Fock (HF) and Kohn-Sham (KS) states as analytical functions of the external potential, $\Delta v$, and of the interaction strength, $U$. We use this…

Chemical Physics · Physics 2022-08-17 Sara Giarrusso , Aurora Pribram-Jones

We present a density difference based analysis for a range of orbital--dependent Kohn--Sham functionals. Results for atoms, some members of the neon isoelectronic series and small molecules are reported and compared with ab initio…

Chemical Physics · Physics 2015-01-22 I. Grabowski , A. M. Teale , E. Fabiano , S. Smiga , A. Buksztel , F. Della Sala

This work presents a theory to unify the two independent theoretical frameworks of Kohn-Sham (KS) density functional theory (DFT) and reduced density matrix functional theory (RDMFT). The generalization of the KS orbitals to hypercomplex…

Chemical Physics · Physics 2021-11-18 Neil Qiang Su

We present and test a new approximation for the exchange-correlation (xc) energy of Kohn-Sham density functional theory. It combines exact exchange with a compatible non-local correlation functional. The functional is by construction free…

Chemical Physics · Physics 2014-05-23 Tobias Schmidt , Eli Kraisler , Adi Makmal , Leeor Kronik , Stephan Kümmel

State specific orbital optimized density functional theory (OO-DFT) methods like restricted open-shell Kohn-Sham (ROKS) can attain semiquantitative accuracy for predicting X-ray absorption spectra of closed-shell molecules. OO-DFT methods…

Chemical Physics · Physics 2022-06-15 Diptarka Hait , Katherine J. Oosterbaan , Kevin Carter-Fenk , Martin Head-Gordon

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

While quantum computers have shown significant promise for electronic structure calculations, their potential to accelerate density functional theory (DFT) calculations remains unclear. In this work, we present a qubit-efficient encoding…

Density-functional theory for superfluid systems is developed in the framework of the functional renormalization group based on the effective action formalism. We introduce the effective action for the particle-number and nonlocal pairing…

Nuclear Theory · Physics 2021-05-11 Takeru Yokota , Haruki Kasuya , Kenichi Yoshida , Teiji Kunihiro

This chapter concerns with the recent development of a new DFT methodology for accurate, reliable prediction of many-electron systems. Background, need for such a scheme, major difficulties encountered, as well as their potential remedies…

Chemical Physics · Physics 2019-04-19 Amlan K. Roy

In periodic systems, the Hartree-Fock (HF) exchange energy exhibits the slowest convergence of all HF energy components as the system size approaches the thermodynamic limit. We demonstrate that the recently proposed staggered mesh method…

Computational Physics · Physics 2024-02-22 Stephen Jon Quiton , Hamlin Wu , Xin Xing , Lin Lin , Martin Head-Gordon

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

Following a recent work [Gal, Phys. Rev. A 64, 062503 (2001)], a simple derivation of the density-functional correction of the Hartree-Fock equations, the Hartree-Fock-Kohn-Sham equations, is presented, completing an integrated view of…

Chemical Physics · Physics 2008-09-11 Tamas Gal

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

Hybrid density functional theory (DFT) remains intractable for large periodic systems due to the demanding computational cost of exact exchange. We apply the tensor hypercontraction (THC) (or interpolative separable density fitting)…

Computational Physics · Physics 2023-10-13 Adam Rettig , Joonho Lee , Martin Head-Gordon

We propose a method for the evaluation of magnetic exchange couplings based on noncollinear spin-density functional calculations. The method employs the second derivative of the total Kohn-Sham energy of a single reference state, in…

Materials Science · Physics 2009-11-13 Juan E. Peralta , Veronica Barone

A previously proposed non-canonical coupled-perturbed Kohn-Sham density functional theory (KS-DFT)/Hartree-Fock (HF) treatment for spin-orbit coupling is here generalized to infinite periodic systems. The scalar-relativistic periodic…

The general procedure underlying Hartree-Fock and Kohn-Sham density functional theory calculations consists in optimizing orbitals for a self-consistent solution of the Roothaan-Hall equations in an iterative process. It is often ignored…

Chemical Physics · Physics 2017-03-16 Alain C. Vaucher , Markus Reiher