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Partition density functional theory is a formally exact procedure for calculating molecular properties from Kohn-Sham calculations on isolated fragments, interacting via a global partition potential that is a functional of the fragment…

Other Condensed Matter · Physics 2015-05-13 Peter Elliott , Kieron Burke , Morrel H. Cohen , Adam Wasserman

We present a new theory for partitioning simulations of periodic and solid-state systems into physically sound atomic contributions at the level of Kohn-Sham density functional theory. Our theory is based on spatially localized linear…

Chemical Physics · Physics 2024-10-01 Luna Zamok , Janus J. Eriksen

We find the numerically exact partition potential for 1-D systems of interacting electrons designed to model diatomic molecules. At integer fragment occupations, the kinetic contribution to the partition potential develops sharp features in…

Chemical Physics · Physics 2018-11-14 Yan Oueis , Adam Wasserman

We illustrate the main features of a recently proposed method based on ensemble density functional theory to divide rigorously a complex molecular system into its parts [M.H. Cohen and A. Wasserman, J. Phys. Chem. A 111, 2229 (2007)]. The…

Other Condensed Matter · Physics 2016-09-28 Morrel H. Cohen , Adam Wasserman , Kieron Burke

Using the optimized effective potential method in conjunction with the semi-analytical approximation due to Krieger, Li and Iafrate, we have performed fully self-consistent exact exchange-only density-functional calculations for diatomic…

chem-ph · Physics 2008-02-03 T. Grabo , E. K. U. Gross

The dissociation of molecules, even the most simple hydrogen molecule, cannot be described accurately within density functional theory because none of the currently available functionals accounts for strong on-site correlation. This problem…

Strongly Correlated Electrons · Physics 2011-01-14 N. Helbig , I. V. Tokatly , A. Rubio

Fromager and Lasorne [Electron. Struct. 6 025002 (2024)] have recently derived an in-principle exact Kohn-Sham density functional theory (KS-DFT) of electrons and nuclei, where the nuclear density and the (so-called conditional) electronic…

Chemical Physics · Physics 2026-03-10 Lucien Dupuy , Benjamin Lasorne , Emmanuel Fromager

The derivative discontinuity of the exchange-correlation functional of density-functional theory is cast as the difference of two types of electron affinities. We show that standard Kohn-Sham calculations can be used to calculate both…

Chemical Physics · Physics 2007-12-13 F. P. Rosselli , A. B. F. da Silva , K. Capelle

We introduce a new approach to density functional theory based on kinetic theory, showing that the Kohn-Sham equations can be derived as a macroscopic limit of a suitable Boltzmann kinetic equation in the limit of small mean free path…

Chemical Physics · Physics 2015-06-15 M. Mendoza , S. Succi , H. J. Herrmann

We model the Hartree-exchange-correlation potential of Kohn-Sham density-functional theory adopting a novel strategy inspired by the strictly-correlated-electrons limit and relying on the exact decomposition of the potential based on the…

Chemical Physics · Physics 2024-09-09 Sara Giarrusso , Federica Agostini

Conceiving a molecule as composed of smaller molecular fragments, or subunits, is one of the pillars of the chemical and physical sciences, and leads to productive methods in quantum chemistry. Using a fragmentation scheme, efficient…

Chemical Physics · Physics 2015-04-14 Martín A. Mosquera , Adam Wasserman

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

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 introduce an orbital free electron density functional approximation based on alchemical perturbation theory. Given convergent perturbations of a suitable reference system, the accuracy of popular self-consistent Kohn-Sham density…

Chemical Physics · Physics 2020-05-27 Guido Falk von Rudorff , O. Anatole von Lilienfeld

In this work we give a comprehensive derivation of an exact and numerically feasible method to perform ab-initio calculations of quantum particles interacting with a quantized electromagnetic field. We present a hierachy of…

We develop a direct derivation for the primary contribution to the vibrational polarizability for molecules, clusters and other finite systems. The vibrational polarizability is then calculated within the generalized gradient approximation…

Other Condensed Matter · Physics 2007-05-23 Mark R. Pederson , Tunna Baruah , Philip B. Allen , Christian Schmidt

Reporting extensions of a recently developed approach to density functional theory with correct long-range be-havior (Phys. Rev. Lett. 94, 043002 (2005)). The central quantities are a splitting functional gamma[n] and a complementary…

Materials Science · Physics 2017-09-13 Ester Livshits , Roi Baer

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

Using a simplified one-dimensional model of a diatomic molecule, the associated interacting density and corresponding Kohn-Sham potential have been obtained analytically for all fractional molecule occupancies $N$ between 0 and 2. For the…

Atomic Physics · Physics 2016-11-15 A. Benitez , C. R. Proetto

A new approach to chemical bonding is introduced in order to provide an improved understanding of the connection between basic quantum mechanics and the covalent pair bond. It's focus is on the fact that the energy of the bond is largely…

Chemical Physics · Physics 2008-02-03 Holger F. Hofmann
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