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We present a new class of non-adiabatic approximations in time-dependent density functional theory derived from an exact expression for the time-dependent exchange-correlation potential. The approximations reproduce dynamical step and peak…

Chemical Physics · Physics 2018-12-21 Lionel Lacombe , Neepa T. Maitra

Ab initio electronic structure methods give accurate results for small systems, but do not scale well to large systems. Chemical insight tells us that molecular functional groups will behave approximately the same way in all molecules,…

Chemical Physics · Physics 2007-05-23 Benjamin G. Janesko , David Yaron

We propose approximations which go beyond the local density approximation for the short-range exchange and correlation density functionals appearing in a multi-determinantal extension of the Kohn-Sham scheme. A first approximation consists…

Chemical Physics · Physics 2009-11-10 Julien Toulouse , Francois Colonna , Andreas Savin

Ideal density-functional approximations (DFAs) should account for dynamic, static, and nondynamic correlation. While common DFAs struggle with the latter two, the Ziegler-Rauk-Baerends-Daul multiplet sum method (MSM) provides a pragmatic…

Chemical Physics · Physics 2026-05-29 Mark E Casida , Abraham Ponra , Gadzikano Munyuki , Bharathi Natarajan

Density functional theory(DFT) and Hartree-Fock(HF) calculations are reported for the family of transition metal fluorides $\mbox{ScF}_3$, $\mbox{TiF}_4$, $\mbox{VF}_5$, and $\mbox{CrF}_6$. Both HF and the local-density-aproximation (LDA)…

chem-ph · Physics 2016-08-31 Thomas V. Russo , Richard L. Martin , P. Jeffrey Hay

Energy barriers, which control the rates of chemical reactions, are seriously underestimated by computationally-efficient semi-local approximations for the exchange-correlation energy. The accuracy of a semi-local density functional…

Chemical Physics · Physics 2023-11-06 Bikash Kanungo , Aaron D. Kaplan , Chandra Shahi , Vikram Gavini , John P. Perdew

We present a rigorous framework that combines single-particle Green's function theory with density functional theory based on a separation of electron-electron interactions into short-range and long-range components. Short-range…

Chemical Physics · Physics 2018-06-07 Alexei A. Kananenka , Dominika Zgid

The fabrication, utilisation, and efficiency of quantum technologies rely on a good understanding of quantum thermodynamic properties. Many-body systems are often used as hardware for these quantum devices, but interactions between…

Strongly Correlated Electrons · Physics 2022-04-26 Krissia Zawadzki , Amy Skelt , Irene D'Amico

Hybrid density functional approximations (DFAs) offer compelling accuracy for ab initio electronic-structure simulations of molecules, nanosystems, and bulk materials, addressing some deficiencies of computationally cheaper, frequently used…

In two recent papers [A. D. Becke, J. Chem. Phys. 156, 214101 (2022) and 157, 234102 (2022)] we compared two Kohn-Sham density functionals based on physical modelling and theory with the best density-functional power-series fits in the…

Chemical Physics · Physics 2023-04-18 Axel D. Becke , Golokesh Santra , Jan M. L. Martin

We introduce a novel non-local ingredient for the construction of exchange density functionals: the reduced Hartree parameter, which is invariant under the uniform scaling of the density and represents the exact exchange enhancement factor…

Other Condensed Matter · Physics 2016-09-04 L. A. Constantin , E. Fabiano , F. Della Sala

Most density functionals have been developed by imposing the known exact constraints on the exchange-correlation energy, or by a fit to a set of properties of selected systems, or by both. However, accurate modeling of the conventional…

Materials Science · Physics 2016-08-24 Jianmin Tao , Yuxiang Mo

We introduce an approximation to the short-range correlation energy functional with multide-terminantal reference involved in a variant of range-separated density-functional theory. This approximation is a local functional of the density,…

Chemical Physics · Physics 2019-03-27 Anthony Ferté , Emmanuel Giner , Julien Toulouse

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

A Neural-Networks-based approach is proposed to construct a new type of exchange-correlation functional for density functional theory. It is applied to improve B3LYP functional by taking into account of high-order contributions to the…

Chemical Physics · Physics 2009-11-10 Xiao Zheng , LiHong Hu , XiuJun Wang , GuanHua Chen

DFT calculations have become widespread in both chemistry and materials, because they usually provide useful accuracy at much lower computational cost than wavefunction-based methods. All practical DFT calculations require an approximation…

Chemical Physics · Physics 2022-03-15 Eunji Sim , Suhwan Song , Stefan Vuckovic , Kieron Burke

Hybrid density functional (HDF) approximations usually deliver higher accuracy than local and semilocal approximations to the exchange-correlation functional, but this comes with drastically increased computational cost. Practical…

Materials Science · Physics 2022-10-12 Yuyang Ji , Peize Lin , Xinguo Ren , Lixin He

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

A widely used approximation to the exchange-correlation functional in density functional theory is the local density approximation (LDA), typically derived from the properties of the homogeneous electron gas (HEG). We previously introduced…

Other Condensed Matter · Physics 2018-06-27 Mike Entwistle , Michele Casula , Rex Godby

The hybrid particle-field molecular dynamics method is an efficient alternative to standard particle-based coarse grained approaches. In this work, we propose an automated protocol for optimisation of the effective parameters that define…

Soft Condensed Matter · Physics 2020-12-02 Morten Ledum , Sigbjørn Løland Bore , Michele Cascella