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We introduce affordable computational strategies for calculating orbital and pair-orbital energies in atomic and molecular systems. Our methods are based on the pair Coupled Cluster Doubles (pCCD) ansatz and its orbital-optimized variant.…

Chemical Physics · Physics 2025-02-06 Seyedehdelaram Jahani , Somayeh Ahmadkhani , Katharina Boguslawski , Paweł Tecmer

Density functional theory (DFT) embedding provides a formally exact framework for interfacing correlated wave-function theory (WFT) methods with lower-level descriptions of electronic structure. Here, we report techniques to improve the…

Chemical Physics · Physics 2015-06-12 Jason D. Goodpaster , Taylor A. Barnes , Frederick R. Manby , Thomas F. Miller

A simple explanation is given for the exactness of the extended Koopmans' theorem for computing the removal energy of any many-electron system to the lowest-energy ground state ion of a given symmetry. In particular, by removing the…

One-body Green's function theories implemented on the real frequency axis offer a natural formalism for the unbiased theoretical determination of quasiparticle spectra in molecules and solids. Self-consistent Green's function methods…

Computational Physics · Physics 2015-05-22 Alicia Rae Welden , Jordan J. Phillips , Dominika Zgid

In orbital-free density functional theory the kinetic potential (KP), the functional derivative of the kinetic energy density functional, appears in the Euler equation for the electron density and may be more amenable to simple…

Other Condensed Matter · Physics 2015-05-13 Jeng-Da Chai , Vincent L. Ligneres , Gregory Ho , Emily A. Carter , John D. Weeks

In the recent work of S. Sharma \emph{et al.}, (arxiv.org: arxiv:0912.1118), a single-electron spectrum associated with the natural orbitals was defined as the derivative of the total energy with respect to the occupation numbers at half…

Chemical Physics · Physics 2012-03-07 E. N. Zarkadoula , S. Sharma , J. K. Dewhurst , E. K. U. Gross , N. N. Lathiotakis

In the exact Kohn-Sham density-functional theory (DFT), the total energy versus the number of electrons is a series of linear segments between integer points. However, commonly used approximate density functionals produce total energies…

Materials Science · Physics 2013-04-03 Eli Kraisler , Leeor Kronik

Polymer self-consistent field theory techniques are used to derive quantum density functional theory without the use of the theorems of density functional theory. Instead, a free energy is obtained from a partition function that is…

Chemical Physics · Physics 2022-11-29 Russell B. Thompson

The piecewise linearity condition on the total energy with respect to the total magnetization of finite quantum systems is derived, using the infinite-separation-limit technique. This generalizes the well-known constancy condition, related…

Strongly Correlated Electrons · Physics 2024-07-22 Andrew C. Burgess , Edward Linscott , David D. O'Regan

We demonstrate in the present study that self-consistent calculations based on the self-energy functional theory (SFT) are possible for the electronic structure of realistic systems in the context of quantum chemistry. We describe the…

Materials Science · Physics 2018-06-14 Taichi Kosugi , Hirofumi Nishi , Yoritaka Furukawa , Yu-ichiro Matsushita

There is a number of explicit kinetic energy density functionals for non-interacting electron systems that are obtained in terms of the electron density and its derivatives. These semilocal functionals have been widely used in the…

Other Condensed Matter · Physics 2011-12-22 David Garcia-Aldea , J. E. Alvarellos

Data-driven spectral analysis of Koopman operators is a powerful tool for understanding numerous real-world dynamical systems, from neuronal activity to variations in sea surface temperature. The Koopman operator acts on a function space…

Numerical Analysis · Mathematics 2025-06-23 Nicolas Boullé , Matthew J. Colbrook , Gustav Conradie

Using a linear combination of atomic orbitals approach, we report a systematic comparison of various Density Functional Theory (DFT) and hybrid exchange-correlation functionals for the prediction of the electronic and structural properties…

Materials Science · Physics 2008-05-07 D. I. Bilc , R. Orlando , R. Shaltaf , G. -M. Rignanese , Jorge Íñiguez , Ph. Ghosez

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

Orbital-Free Density Functional Theory (OF-DFT) promises to describe the electronic structure of very large quantum systems, being its computational cost linear with the system size. However, the OF-DFT accuracy strongly depends on the…

Chemical Physics · Physics 2018-06-06 L. A. Constantin , E. Fabiano , F. Della Sala

We report an analytical representation of the correlation energy ec(rs, zeta) for a uniform electron gas (UEG), where rs is the Seitz radius or density parameter and zeta is the relative spin polarization. The new functional, called W20, is…

Chemical Physics · Physics 2021-01-27 Qing-Xing Xie , Jiashun Wu , Yan Zhao

In this paper, we propose a generic and systematic approach for study of the electronic structure for atoms or molecules. In particular, we address the issue of single particle states, or orbitals, which should be one of the most important…

Chemical Physics · Physics 2007-05-23 Liqiang Wei

Within exact electron density-functional theory, we investigate Kohn-Sham (KS) potentials, orbital energies, and non-interacting kinetic energies of the fractional ions of Li, C and F. We use quantum Monte Carlo densities as input, which…

Chemical Physics · Physics 2014-11-14 Tim Gould , Julien Toulouse

We present $\vec{k}$-dependent one-particle spectra and corresponding effective bandstructures for the $2d$ Hubbard model calculated within the dynamical molecular field theory (DMFT). This method has proven to yield highly nontrivial…

Condensed Matter · Physics 2016-08-31 Th. Pruschke , Th. Obermeier , J. Keller , M. Jarrell

Kinetic energy (KE) approximations are key elements in orbital-free density functional theory. To date, the use of non-local functionals, possibly employing system dependent parameters, has been considered mandatory in order to obtain…

Materials Science · Physics 2018-07-25 L. A. Constantin , E. Fabiano , F. Della Sala