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Functionals that explicitly depend on occupied, unoccupied, or fractionally-occupied orbitals are rigorously formalized using Clifford algebras, and a variational principle is established that facilitates orbital (and occupation)…

Quantum Physics · Physics 2024-04-26 Neil Qiang Su

A description of non-collinear magnetism in the framework of spin-density functional theory is presented for the exact exchange energy functional which depends explicitly on two-component spinor orbitals. The equations for the effective…

The relation between the derivative of the energy with respect to occupation number and the orbital energy, $\partial E/\partial n_i = \epsilon_i$, was first introduced by Slater for approximate total energy expressions such as Hartree-Fock…

Chemical Physics · Physics 2019-11-14 Evert Jan Baerends

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

A direct orbital optimization method is presented for density functional calculations of excited electronic states using either a real space grid or a plane wave basis set. The method is variational, provides atomic forces in the excited…

Computational Physics · Physics 2022-11-09 Aleksei V. Ivanov , Gianluca Levi , Elvar Ö. Jónsson , Hannes Jónsson

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

The exact formulation of multi-configuration density-functional theory (DFT) is discussed in this work. As an alternative to range-separated methods, where electron correlation effects are split in the coordinate space, the combination of…

Chemical Physics · Physics 2015-02-26 Emmanuel Fromager

The universal functional of Hohenberg-Kohn is given as a coupling-constant integral over the density as a functional of the potential. Conditions are derived under which potential-functional approximations are variational. Construction via…

Other Condensed Matter · Physics 2011-06-13 Attila Cangi , Donghyung Lee , Peter Elliott , Kieron Burke , E. K. U. Gross

We consider density functionals for exchange and correlation energies in two-dimensional systems. The functionals are constructed by making use of exact constraints for the angular averages of the corresponding exchange and correlation…

Strongly Correlated Electrons · Physics 2010-02-25 E. Rasanen , S. Pittalis

We introduce a new functional for simulating ground-state and time-dependent electronic systems within density-functional theory. The functional combines an expression for the exact Kohn-Sham (KS) potential in the limit of complete electron…

Mesoscale and Nanoscale Physics · Physics 2021-01-15 M. J. P. Hodgson , J. D. Ramsden , T. R. Durrant , R. W. Godby

First-principles calculations based on density functional theory have been widely used in studies of the structural, thermoelastic, rheological, and electronic properties of earth-forming materials. The exchange-correlation term, however,…

Computational Physics · Physics 2009-11-13 S. H. Lee , Jones T. K. Wan

Fractional occupation numbers can produce open-shell degeneracy in density functional theory. We develop the corresponding perturbation theory by requiring that a differentiable map connects the initial and perturbed states. The degenerate…

Materials Science · Physics 2016-07-22 Mark C. Palenik , Brett I. Dunlap

We introduce an energy functional for ground-state electronic structure calculations. Its variables are the natural spin-orbitals of singlet many-body wave functions and their joint occupation probabilities deriving from controlled…

Chemical Physics · Physics 2016-12-04 Ralph Gebauer , Morrel H. Cohen , Roberto Car

The standard way to calculate the Kohn-Sham orbitals utilizes an approximation of the potential. The approximation consists in a projection of the potential into a finite subspace of basis functions. The orbitals, calculated with the…

Computational Physics · Physics 2018-11-19 Rudolf Zeller

In the context of the density functional theory we consider the single particle excitation spectra of electron systems. As a result, we have related the single particle excitations with the eigenvalues of the corresponding Kohn-Sham…

Condensed Matter · Physics 2009-10-31 M. Ya. Amusia , V. R. Shaginyan

Modern extensions of density functional theory such as the density functional theory plus U and the density functional theory plus dynamical mean-field theory require choices, including selection of variable (charge vs spin density) for the…

Strongly Correlated Electrons · Physics 2015-05-04 Hyowon Park , Andrew J. Millis , Chris A. Marianetti

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…

Chemical Physics · Physics 2018-01-03 Yasumitsu Suzuki , Lionel Lacombe , Kazuyuki Watanabe , Neepa T. Maitra

Standard approximations for the exchange-correlation functional are known to deviate from linear dependence of the energy on the electron and spin numbers (in -space). Violation of this flat-plane condition underlies the failure of all…

Classical Physics · Physics 2013-10-28 Ali M. Malek , Robert Balawender

Specific matrix elements of exchange and correlation kernels in time-dependent density-functional theory are computed. The knowledge of these matrix elements not only constraints approximate time-dependent functionals, but also allows to…

Materials Science · Physics 2009-10-31 X. Gonze , M. Scheffler

We use the exact strong-interaction limit of the Hohenberg-Kohn energy density functional to approximate the exchange-correlation energy of the restricted Kohn-Sham scheme. Our approximation corresponds to a highly non-local density…

Strongly Correlated Electrons · Physics 2012-12-12 Francesc Malet , Paola Gori-Giorgi