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Time-dependent Hartree-Fock (TDHF) is one of the fundamental post-Hartree-Fock (HF) methods to describe excited states. In its Tamm-Dancoff form, equivalent to Configuration Interaction Singles, it is still widely used and particularly…

Chemical Physics · Physics 2024-11-18 Uday Panta , David A. Strubbe

Following Hollins et al. [J. Phys.: Condens. Matter 29, 04LT01 (2017)], we invert the electronic ground state densities for various semiconducting and insulating solids calculated using several density functional approximations within the…

Chemical Physics · Physics 2025-11-05 Visagan Ravindran , Nikitas I. Gidopoulos , Stewart J. Clark

A long-standing puzzle in density-functional theory is the issue of the long-range behavior of the Kohn-Sham exchange-correlation potential at metal surfaces. As an important step towards its solution, it is proved here, through a rigurouos…

Materials Science · Physics 2015-05-18 C. M. Horowitz , C. R. Proetto , J. M. Pitarke

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

Quasiparticle energies and fundamental band gaps in particular are critical properties of molecules and materials. It was rigorously established that the generalized Kohn-Sham HOMO and LUMO orbital energies are the chemical potentials of…

Chemical Physics · Physics 2019-03-06 Yuncai Mei , Chen Li , Neil Qiang Su , Weitao Yang

Coupled cluster calculations are traditionally performed over Hartree-Fock reference orbitals (HF-CC methodology). However, it has been repeatedly argued in the literature that the use of a Kohn-Sham reference (KS-CC methodology) might…

Chemical Physics · Physics 2025-03-10 Zsolt Benedek , Paula Tímár , Tibor Szilvási , Gergely Barcza

Exact exchange (EXX) Kohn-Sham calculations within an all-electron full-potential method are performed on a range of semiconductors and insulators (Ge, GaAs, CdS, Si, ZnS, C, BN, Ne, Ar, Kr and Xe). We find that the band-gaps are not as…

Materials Science · Physics 2009-11-11 S. Sharma , J. K. Dewhurst , C. Ambrosch-Draxl

We present a novel energy-based localization procedure able to localize molecular orbitals into specific spatial regions. The method is applied to several cases including both conjugated and non-conjugated systems. The obtained localized…

Chemical Physics · Physics 2022-09-13 Tommaso Giovannini , Henrik Koch

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

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

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

The concept of the effective one-electron potentials (OEP) has been useful for many decades in efficient description of electronic structure of chemical systems, especially extended molecular aggregates such as interacting molecules in…

Chemical Physics · Physics 2020-02-04 Bartosz Błasiak , Joanna D. Bednarska , Marta Chołuj , Wojciech Bartkowiak

An explicitly orbital-dependent correlation energy functional is proposed, which is to be used in combination with the orbital-dependent exchange energy functional in energy-band calculations. It bears a close resemblance to the…

Strongly Correlated Electrons · Physics 2009-11-10 Masahiko Higuchi , Hiroshi Yasuhara

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

In this article, we consider the extended Kohn-Sham model for atoms subjected to cylindrically-symmetric external potentials. The variational approximation of the model and the construction of appropriate discretization spaces are detailed…

Mathematical Physics · Physics 2018-07-04 Eric Cancès , Nahia Mourad

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 Ryabinkin-Kohut-Staroverov (RKS) and Kanungo-Zimmerman-Gavini (KZG) methods offer two approaches to find exchange-correlation (XC) potentials from ground state densities. The RKS method utilizes the one- and two-particle reduced density…

Chemical Physics · Physics 2024-08-06 Bikash Kanungo , Soumi Tribedi , Paul M. Zimmerman , Vikram Gavini

We have examined the performance of the analytic Hartree-Fock-Slater (HFS) method for various alpha (Slater's exchange parameter) values and empiricaly determined the optimal alpha value by minimizing the mean absolute error (MAE) in…

Other Condensed Matter · Physics 2016-08-31 Rajendra R. Zope , Brett I. Dunlap

We incorporate in the Kohn-Sham self consistent equation a trained neural-network projection from the charge density distribution to the Hartree-exchange-correlation potential $n \rightarrow V_{\rm Hxc}$ for possible numerical approach to…

Computational Physics · Physics 2018-07-04 Ryo Nagai , Ryosuke Akashi , Shu Sasaki , Shinji Tsuneyuki

Reliable computational methodologies and basis sets for modeling x-ray spectra are essential for extracting and interpreting electronic and structural information from experimental x-ray spectra. In particular, the trade-off between…

Chemical Physics · Physics 2025-03-26 Alexis A. A. Delgado , Devin A. Matthews