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A new density functional theory (DFT) exchange-correlation functional for the exploration of reaction mechanisms is proposed. This new functional, denoted BMK (Boese-Martin for Kinetics), has an accuracy in the 2 kcal/mol range for…

Chemical Physics · Physics 2007-05-23 A. Daniel Boese , Jan M. L. Martin

The standard (``fine-grained'') interpretation of quantum density functional theory, in which densities are specified with infinitely-fine spatial resolution, is mathematically unruly. Here, a coarse-grained version of DFT, featuring…

Mathematical Physics · Physics 2015-05-13 Paul E. Lammert

Orbital-free density functional theory (OF-DFT) constitutes a computationally highly effective tool for modeling electronic structures of systems ranging from room-temperature materials to warm dense matter. Its accuracy critically depends…

Potential functional approximations are an intriguing alternative to density functional approximations. The potential functional that is dual to the Lieb density functional is defined and properties given. The relationship between…

Other Condensed Matter · Physics 2014-01-08 Attila Cangi , E. K. U. Gross , Kieron Burke

We argue that the success of DFT can be understood in terms of a semiclassical expansion around a very specific limit. This limit was identified long ago by Lieb and Simon for the total electronic energy of a system. This is a universal…

Chemical Physics · Physics 2021-05-18 Pavel Okun , Kieron Burke

The construction of meta generalized gradient approximations based on the density matrix expansion (DME) is considered as one of the most accurate technique to design semilocal exchange energy functionals in two-dimensional density…

Materials Science · Physics 2018-05-09 Abhilash Patra , Subrata Jana , Prasanjit Samal

Density functional theory (DFT) provides a theoretical framework for efficient and fairly accurate calculations of the electronic structure of molecules and crystals. The main features of density functional theory are described and DFT…

Chemical Physics · Physics 2012-06-12 Hauke Paulsen , Alfred Xaver Trautwein

An accurate expression of the kinetic energy density of an electronic distribution in terms of the single particle reduced density matrix for atomic and molecular systems is a long-standing problem in electron structure theory. Existing…

Chemical Physics · Physics 2024-10-30 Priya , Mainak Sadhukhan

The crucial step in density-corrected Hartree-Fock density functional theory (DC(HF)-DFT) is to decide whether the density produced by the density functional for a specific calculation is erroneous and hence should be replaced by, in this…

Chemical Physics · Physics 2023-09-20 Daniel Graf , Alex J. W. Thom

Due to several attractive features, the meta-generalized-gradient approximations (meta-GGAs) are considered to be the most advanced and potentially accurate semilocal exchange-correlation functionals in the rungs of the Jacob's ladder of…

Atomic and Molecular Clusters · Physics 2020-04-28 Abhilash Patra , Subrata Jana , Lucian A. Constantin , Prasanjit Samal

From a simplified version of the mathematical structure of the strong coupling limit of the exact exchange-correlation functional, we construct an approximation for the electronic repulsion energy at physical coupling strength, which is…

Chemical Physics · Physics 2017-05-11 Stefan Vuckovic , Paola Gori-Giorgi

We establish the theoretical foundations for embedding a correlated wave function in an environment formed by Kohn-Sham orbitals. We show that introducing an approximation which equates two, in principle distinct, kinetic-energy functionals…

Chemical Physics · Physics 2026-03-06 Enzo Monino , Daria Drwal , Michał Hapka , Libor Veis , Katarzyna Pernal

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

We performed density functional calculations to estimate the formation energies of intermetallic alloys. We used two semilocal approximations, the generalized gradient approximation (GGA) by Perdew-Burke-Ernzerhof (PBE) and the strongly…

Materials Science · Physics 2020-11-25 Niraj K. Nepal , Santosh Adhikari , Bimal Neupane , Adrienn Ruzsinszky

Gross--Oliveira--Kohn (GOK) ensemble density-functional theory (GOK-DFT) is a time-\textit{independent} extension of density-functional theory (DFT) which allows to compute excited-state energies via the derivatives of the ensemble energy…

Chemical Physics · Physics 2020-06-18 Clotilde Marut , Bruno Senjean , Emmanuel Fromager , Pierre-François Loos

Classical density functional theory (DFT) is a powerful framework to study inhomogeneous fluids. Its standard form is based on the knowledge of a generating free energy functional. If this is known exactly, then the results obtained by…

Soft Condensed Matter · Physics 2025-05-02 S. M. Tschopp , H. Vahid , A. Sharma , J. M. Brader

We investigate a highly-nonlocal generalization of the Lindhard function, given by the jellium-with-gap model. We find a band-gap-dependent gradient expansion of the kinetic energy, which performs noticeably well for large atoms. Using the…

Other Condensed Matter · Physics 2017-05-18 L. A. Constantin , E. Fabiano , S. Śmiga , F. Della Sala

The formally exact framework of equilibrium Density Functional Theory (DFT) is capable of simultaneously and consistently describing thermodynamic and structural properties of interacting many-body systems in arbitrary external potentials.…

The widespread use of (generalized) Kohn-Sham density functional theory (KS-DFT) lies in the fact that hierarchical sets of approximations of the exchange-correlation (XC) energy functional can be designed, offering versatile choices to…

Materials Science · Physics 2023-01-31 Igor Ying Zhang , Xinguo Ren

Multicomponent density functional theory (DFT) enables the consistent quantum mechanical treatment of both electrons and protons. A major challenge has been the design of electron-proton correlation functionals that produce even…

Chemical Physics · Physics 2017-09-26 Yang Yang , Kurt R. Brorsen , Tanner Culpitt , Michael V. Pak , Sharon Hammes-Schiffer