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Delocalization errors, such as charge-transfer and some self-interaction errors, plague computationally-efficient and otherwise-accurate density functional approximations (DFAs). Evaluating a semi-local DFA non-self-consistently on the…

Chemical Physics · Physics 2023-01-02 Aaron D. Kaplan , Chandra Shahi , Pradeep Bhetwal , Raj K. Sah , John P. Perdew

We derive a non-empirical, orbital-free density functional for the total energy of interacting electrons in two dimensions. The functional consists of a local formula for the interaction energy, where we follow the lines introduced by Parr…

Strongly Correlated Electrons · Physics 2009-10-09 S. Pittalis , E. Rasanen

Density functional theory (DFT), one of the most widely utilized methods available to computational chemistry, fails to describe systems with statically correlated electrons. To address this shortcoming, in previous work we transformed DFT…

Chemical Physics · Physics 2023-01-02 Daniel Gibney , Jan-Niklas Boyn , David A. Mazziotti

We present an \emph{Effective Static Approximation} (ESA) to the local field correction (LFC) of the electron gas that enables highly accurate calculations of electronic properties like the dynamic structure factor $S(q,\omega)$, the static…

Empirical fitting of parameters in approximate density functionals is common. Such fits conflate errors in the self-consistent density with errors in the energy functional, but density-corrected DFT (DC-DFT) separates these two. We…

Chemical Physics · Physics 2020-12-02 Suhwan Song , Stefan Vuckovic , Eunji Sim , Kieron Burke

The complete active space self-consistent field (CASSCF) method is the principal approach employed for studying strongly correlated systems. However, exact CASSCF can only be performed on small active spaces of ~20 electrons in ~20 orbitals…

Computational Physics · Physics 2021-12-22 Daniel S. Levine , Diptarka Hait , Norm M. Tubman , Susi Lehtola , K. Birgitta Whaley , Martin Head-Gordon

Perdew-Zunger self-interaction correction (PZ-SIC) offers a route to remove self-interaction errors on an orbital-by-orbital basis. A recent formulation of PZ-SIC by Pederson, Ruzsinszky and Perdew proposes restricting the unitary…

Chemical Physics · Physics 2021-12-07 Carlos M. Diaz , Tunna Baruah , Rajendra R. Zope

An accurate analytical parametrization for the exchange-correlation free energy of the homogeneous electron gas, including interpolation for partial spin-polarization, is derived via thermodynamic analysis of recent restricted path integral…

Chemical Physics · Physics 2015-06-17 Valentin V. Karasiev , Travis Sjostrom , James Dufty , S. B. Trickey

For the treatment of interacting electrons in crystal lattices approximations based on the picture of effective sites, coupled in a self-consistent fashion, have proven very useful. Particularly in the presence of strong local correlations,…

Strongly Correlated Electrons · Physics 2008-09-19 Norbert Grewe , Sebastian Schmitt , Torben Jabben , Frithjof B. Anders

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

We introduce a new method for deriving the time-dependent Hartree or Hartree-Fock equations as an effective mean-field dynamics from the microscopic Schroedinger equation for fermionic many-particle systems in quantum mechanics. The method…

Mathematical Physics · Physics 2016-11-29 Sören Petrat , Peter Pickl

We discuss a possible form for a theory akin to local density functional theory, but able to produce van der Waals energies in a natural fashion. The usual Local Density Approximation (LDA) for the exchange and correlation energy $E_{xc}$…

Soft Condensed Matter · Physics 2007-05-23 John F. Dobson

Analytical expressions for the binding energy of electrons and positrons in dielectric clusters, analysed in this work, neglect the elastic effects. Therefore, we present the density-functional theory for neutral liquid clusters that…

Mesoscale and Nanoscale Physics · Physics 2007-05-23 Valentin V. Pogosov , Walter V. Pogosov , Denis P. Kotlyarov

We introduce a new functional for simulating ground-state and time-dependent electronic systems within density-functional theory. The functional combines an expression for the exact Kohn-Sham (KS) potential in the limit of complete electron…

Mesoscale and Nanoscale Physics · Physics 2021-01-15 M. J. P. Hodgson , J. D. Ramsden , T. R. Durrant , R. W. Godby

We present an accurate local density-functional for electronic-structure calculations within the density functional theory (DFT). The functional is derived by analyzing the structure of the standard perturbative expansion of the correlation…

Materials Science · Physics 2024-11-28 Mario Benites , Angel Rosado , Efstratios Manousakis

XYG3-type doubly hybrid approximations (xDH) have gained a widespread recognition for their accuracy in describing a diverse range of chemical and physical interactions. However, a recent study (J. Phys. Chem. 2021, 12, 800-807) has…

Chemical Physics · Physics 2024-01-10 Sheng Bi , Shirong Wang , Igor Ying Zhang , Xin Xu

The charge delocalization error, besides nondynamic correlation, has been a major challenge to density functional theory. Contemporary functionals undershoot the dissociation of symmetric charged dimers A2+, a simple but stringent test,…

Chemical Physics · Physics 2021-07-26 Emil Proynov , Jing Kong

We introduce 1-RDMFT in the canonical ensemble and then proceed to approximate the interacting ensemble by a non-interacting ensemble that maximizes the entropy, independently of temperature. Bosonic and Fermionic Sinkhorn algorithms are…

Chemical Physics · Physics 2022-05-31 Derk P. Kooi

We present a fully variational generalization of the pseudo self-interaction correction (VPSIC) approach previously presented in two implementations based on plane-waves and atomic orbital basis set, known as PSIC and ASIC, respectively.…

Materials Science · Physics 2015-05-28 A. Filippetti , C. D. Pemmaraju , P. Delugas , D. Puggioni , V. Fiorentini , S. Sanvito

The isostructural {\alpha}-{\gamma} phase transition in cerium is analyzed using density-functional theory with different exchange-correlation functionals, in particular the PBE0 hybrid functional and the exact- exchange plus correlation in…

Strongly Correlated Electrons · Physics 2015-06-11 Marco Casadei , Xinguo Ren , Patrick Rinke , Angel Rubio , Matthias Scheffler
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