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The accurate description of open-shell molecules, in particular of transition metal complexes and clusters, is still an important challenge for quantum chemistry. While density-functional theory (DFT) is widely applied in this area, the…

Chemical Physics · Physics 2012-10-26 Christoph R. Jacob , Markus Reiher

We employ reduced density-matrix functional theory in the calculation of the fundamental gap of open-shell systems. The formula for the calculation of the fundamental gap is derived with special attention to the spin of the neutral and the…

Materials Science · Physics 2011-01-14 N. Helbig , N. N. Lathiotakis , E. K. U. Gross

Using the newly introduced theory of finite-temperature reduced density matrix functional theory, we apply the first-order approximation to the homogeneous electron gas. We consider both collinear spin states as well as symmetry broken…

Strongly Correlated Electrons · Physics 2015-03-20 Tim Baldsiefen , F. G. Eich , E. K. U. Gross

By introducing the self-energy density functionals for the dissipative interactions between the reduced system and its environment, we develop a time-dependent density-functional theory formalism based on an equation of motion for the…

Quantum Physics · Physics 2009-11-13 Xiao Zheng , Fan Wang , Chi Yung Yam , Yan Mo , GuanHua Chen

We apply reduced density-matrix functional theory to the parabolically confined quantum Hall droplet in the spin-frozen strong magnetic field regime. One-body reduced density matrix functional method performs remarkably well in obtaining…

Mesoscale and Nanoscale Physics · Physics 2015-05-14 E. Tölö , A. Harju

According to the Hohenberg-Kohn theorem of density-functional theory (DFT), all observable quantities of systems of interacting electrons can be expressed as functionals of the ground-state density. This includes, in principle, the spin…

Strongly Correlated Electrons · Physics 2019-09-04 Carsten A. Ullrich

Based on our derivation of finite temperature reduced density matrix functional theory and the discussion of the performance of its first-order functional this work presents several different correlation-energy functionals and applies them…

Other Condensed Matter · Physics 2012-08-24 Tim Baldsiefen , E. K. U. Gross

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

We prove that the electron density function of a real physical system can be uniquely determined by its values on any finite subsystem. This establishes the existence of a rigorous density-functional theory for any open electronic system.…

Quantum Physics · Physics 2007-05-23 Xiao Zheng , Fan Wang , GuanHua Chen

We consider density functionals for exchange and correlation energies in two-dimensional systems. The functionals are constructed by making use of exact constraints for the angular averages of the corresponding exchange and correlation…

Strongly Correlated Electrons · Physics 2010-02-25 E. Rasanen , S. Pittalis

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

In this work we explore the performance of approximations to electron correlation in reduced density-matrix functional theory (RDMFT) and of approximations to the observables calculated within this theory. Our analysis focuses on the…

Strongly Correlated Electrons · Physics 2015-02-26 Stefano Di Sabatino , Jan A. Berger , Lucia Reining , Pina Romaniello

The problem of degenerate ground states of open-shell atoms is investigated in spin-restricted and unrestricted density functional theory using the exact exchange energy functional. For the spin-unrestricted case, spurious energy splittings…

Atomic Physics · Physics 2009-11-11 S. Pittalis , S. Kurth , E. K. U. Gross

A fermion ground state energy functional is set up in terms of particle density, relative pair density, and kinetic energy tensor density. It satisfies a minimum principle if constrained by a complete set of compatibility conditions. A…

Chemical Physics · Physics 2009-10-17 Bin Liu , Jerome K. Percus

The reconstruction of the exchange-correlation potential from accurate ab initio electron densities can provide insights into the limitations of the currently available approximate functionals and provide guidance for devising improved…

Strongly Correlated Electrons · Physics 2013-02-05 Katharina Boguslawski , Christoph R. Jacob , Markus Reiher

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

The quest for an approximate yet accurate kinetic energy density functional is central to the development of orbital-free density functional theory. While a recipe for closed-shell systems has been proposed earlier, we have shown that it…

Chemical Physics · Physics 2022-08-15 Priya Priya , Mainak Sadhukhan

Reduced density matrix functional theory for the case of solids is presented and a new exchange correlation functional based on a fractional power of the density matrix is introduced. We show that compared to other functionals, this…

Materials Science · Physics 2009-11-13 S. Sharma , J. K. Dewhurst , N. N. Lathiotakis , E. K. U. Gross

Electrons in zero external magnetic field can be studied with density functional theory (DFT) or with spin-DFT (SDFT). The latter is normally used for open shell systems because its approximations appear to model better the exchange and…

Chemical Physics · Physics 2022-04-06 Timothy Callow , Benjamin Pearce , Nikitas Gidopoulos

We introduce a novel energy functional for ground-state electronic-structure calculations. Its fundamental variables are the natural spin-orbitals of the implied singlet many-body wave function and their joint occupation probabilities. The…

Chemical Physics · Physics 2015-06-23 Ralph Gebauer , Morrel H. Cohen , Roberto Car
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