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Fractional occupation numbers can be used in density functional theory to create a symmetric Kohn-Sham potential, resulting in orbitals with degenerate eigenvalues. We develop the corresponding perturbation theory and apply it to a system…

Materials Science · Physics 2016-09-09 Mark C. Palenik , Brett I. Dunlap

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

Orbital relaxation of the core region is a primary source of error in the computation of core ionization and core excitation energies. Recently, Transition-Potential Coupled Cluster (TP-CC) methods have been used to explicitly treat orbital…

Chemical Physics · Physics 2025-03-17 Alexis A. A. Delgado , Devin A. Matthews

This chapter provides a comprehensive review of fundamental concepts related to approximate natural orbital functionals (NOFs), emphasizing their significance in quantum chemistry and physics. Focusing on fermions, the discussion excludes…

Chemical Physics · Physics 2023-12-13 Mario Piris

Within the framework of natural orbital functional theory, having a convenient representation of the occupation numbers and orbitals becomes critical for the computational performance of the calculations. Recognizing this, we propose an…

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 route to reliable quantum nanoelectronic devices hinges on precise control of the electrostatic environment. For this reason, accurate methods for electrostatic simulations are essential in the design process. The most widespread…

Mesoscale and Nanoscale Physics · Physics 2023-02-28 Waldemar Svejstrup , Andrea Maiani , Kevin Van Hoogdalem , Karsten Flensberg

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

Natural orbital functional (NOF) theory offers a promising approach for studying strongly correlated systems at an affordable computational cost, with an accuracy comparable to highly demanding wavefunction-based methods. However, its…

Strongly Correlated Electrons · Physics 2025-01-31 Juan Felipe Huan Lew-Yee , Jorge M. del Campo , Mario Piris

By introducing a set of auxiliary equations representing a many-body system, we have derived an extension of the Kohn-Sham scheme for the density functional theory. These equations consist of a Kohn-Sham-type equation determining…

Materials Science · Physics 2009-11-07 Koichi Kusakabe

Within the framework of linear-scaling Kohn-Sham density functional theory, a robust method for maintaining compact localized orbitals close to the ground state is coupled with nuclear dynamics. This allows to obviate the commonly employed…

Computational Physics · Physics 2018-08-01 Hayden Scheiber , Yifei Shi , Rustam Z. Khaliullin

Spin-current density functional theory (SCDFT) is a formally exact framework designed to handle the treatment of interacting many-electron systems including spin-orbit coupling at the level of the Pauli equation. In practice, robust and…

Clifford geometric algebras of multivectors are treated in detail. These algebras are build over a graded space and exhibit a grading or multivector structure. The careful study of the endomorphisms of this space makes it clear, that…

High Energy Physics - Theory · Physics 2015-06-26 Bertfried Fauser

A new method is presented that allows for efficient evaluation of spin-orbit coupling (SOC) in density-functional theory calculations. In the so-called second-variational scheme, where Kohn-Sham functions obtained in a scalar-relativistic…

Materials Science · Physics 2023-06-06 Cecilia Vona , Sven Lubeck , Hannah Kleine , Andris Gulans , Claudia Draxl

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

We present a rigorous formulation of generalized Kohn-Sham density-functional theory. This provides a straightforward Kohn-Sham description of many-body systems based not only on particle-density but also on any other observable. We…

Strongly Correlated Electrons · Physics 2008-02-03 M. Valiev , G. W. Fernando

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…

This manuscript gives a theoretical framework for a new Hilbert space of functions, the so called occupation kernel Hilbert space (OKHS), that operate on collections of signals rather than real or complex numbers. To support this new…

Functional Analysis · Mathematics 2022-04-19 Joel A. Rosenfeld , Benjamin Russo , Xiuying Li

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

Spatially localized one-electron orbitals, orthogonal and nonorthogonal, are widely used in electronic structure theory to describe chemical bonding and speed up calculations. In order to avoid linear dependencies of localized orbitals, the…

Chemical Physics · Physics 2020-03-04 Ziling Luo , Rustam Z. Khaliullin