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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

The exchange-correlation energy in Kohn-Sham density functional theory can be expressed exactly in terms of the change in the expectation of the electron-electron repulsion operator when, in the many-electron hamiltonian, this same operator…

Strongly Correlated Electrons · Physics 2009-08-05 Paola Gori-Giorgi , Giovanni Vignale , Michael Seidl

Mejia-Rodriguez and Trickey recently proposed a procedure for removing the explicit dependence of meta-GGA exchange-correlation energy functionals $E_{\rm xc}$ on the kinetic energy density $\tau$. We present a simple modification to this…

Materials Science · Physics 2024-04-22 Pietro Bonfà , Sangeeta Sharma , John Kay Dewhurst

The kinetic energy (KE) kernel, which is defined as the second order functional derivative of the KE functional with respect to density, is the key ingredient to the construction of KE models for orbital free density functional theory…

Materials Science · Physics 2025-05-15 Zhandos A. Moldabekov , Xuecheng Shao , Michele Pavanello , Jan Vorberger , Tobias Dornheim

Density functional theory (DFT) and beyond-DFT methods are often used in combination with photoelectron spectroscopy to obtain physical insights into the electronic structure of molecules and solids. The Kohn-Sham eigenvalues are not…

We resolve a fundamental issue associated with the conventional Kohn-Sham formulation of real-time time-dependent density functional theory. We show that unphysical multielectron excitations, generated during time propagation of the…

Computational Physics · Physics 2020-01-16 Xiaoning Zang , Udo Schwingenschlogl , Mark T. Lusk

Using principles of asymptotic analysis, we derive the exact leading corrections to the Thomas-Fermi kinetic energy approximation for Kohn-Sham electrons for slabs. This asymptotic expansion approximation includes crucial quantum…

Materials Science · Physics 2024-02-21 Pavel Okun , Antonio C. Cancio , Kieron Burke

From the perspective of perturbation theory, we propose a systematic procedure for the evaluation of the derivative discontinuity (DD) of the exchange-correlation energy functional in Kohn-Sham density functional theory (KS-DFT), wherein…

Chemical Physics · Physics 2013-01-17 Jeng-Da Chai , Po-Ta Chen

The uniform electron gas and the hydrogen atom play fundamental roles in condensed matter physics and quantum chemistry. The former has an infinite number of electrons uniformly distributed over the neutralizing positively-charged…

Chemical Physics · Physics 2016-06-22 Jianwei Sun , John P. Perdew , Zenghui Yang , Haowei Peng

In this paper, we investigate the energy minimization model of the ensemble Kohn-Sham density functional theory for metallic systems, in which a pseudo-eigenvalue matrix and a general smearing approach are involved. We study the invariance…

Numerical Analysis · Mathematics 2022-01-19 Xiaoying Dai , Stefano de Gironcoli , Bin Yang , Aihui Zhou

In contrast to the original Kohn-Sham (KS) formalism, we propose a density functional theory (DFT) with fractional orbital occupations for the study of ground states of many-electron systems, wherein strong static correlation is shown to be…

Chemical Physics · Physics 2015-06-03 Jeng-Da Chai

We study the asymptotic expansion of the neutral-atom energy as the atomic number Z goes to infinity, presenting a new method to extract the coefficients from oscillating numerical data. We find that recovery of the correct expansion is an…

Atomic and Molecular Clusters · Physics 2009-11-13 Donghyung Lee , Kieron Burke , Lucian A. Constantin , John P. Perdew

Based on the time-dependent density-functional theory, we have derived a rigorous formula for the stopping power of an {\it interacting} electron gas for ions in the limit of low projectile velocities. If dynamical correlation between…

Materials Science · Physics 2009-11-11 V. U. Nazarov , J. M. Pitarke , C. S. Kim , Y. Takada

The correlation energy in density functional theory can be expressed exactly in terms of the change in the probability of finding two electrons at a given distance $r_{12}$ (intracule density) when the electron-electron interaction is…

Other Condensed Matter · Physics 2017-08-23 Paola Gori-Giorgi , Michael Seidl , Andreas Savin

The polarization-dependence of the exchange-correlation (XC) energy functional of periodic insulators within Kohn-Sham (KS) density-functional theory requires a ${\cal O} (1/q^2)$ divergence in the XC kernel for small vectors q. This…

Materials Science · Physics 2009-10-30 Ph. Ghosez , X. Gonze , R. W. Godby

In this paper, we present a completely rigorous formulation of Kohn-Sham density functional theory for spinless fermions living in one dimensional space. More precisely, we consider Schr\"odinger operators of the form $H_N(v,w) = -\Delta +…

Mathematical Physics · Physics 2026-03-24 Thiago Carvalho Corso

Kohn-Sham regularizer (KSR) is a differentiable machine learning approach to finding the exchange-correlation functional in Kohn-Sham density functional theory (DFT) that works for strongly correlated systems. Here we test KSR for weak…

Chemical Physics · Physics 2022-03-22 Bhupalee Kalita , Ryan Pederson , Jielun Chen , Li Li , Kieron Burke

Kohn-Sham density functional theory calculations using conventional diagonalization based methods become increasingly expensive as temperature increases due to the need to compute increasing numbers of partially occupied states. We present…

Chemical Physics · Physics 2022-03-23 Qimen Xu , Xin Jing , Boqin Zhang , John E. Pask , Phanish Suryanarayana

One of the most important open challenges in modern Kohn-Sham (KS) density-functional theory (DFT) is the correct treatment of fractional electron charges and spins. Approximate exchange-correlation (XC) functionals struggle to do this in a…

Chemical Physics · Physics 2015-12-24 Jonathan Nafziger , Adam Wasserman

A partial differential eigenvalue equation for the density displacement fields associated with electronic excitations is derived in the framework of density functional theory. Our quantum fluid-dynamical approach is based on a variational…

Atomic and Molecular Clusters · Physics 2009-11-07 S. Kümmel , M. Brack