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We explore the impact of optimizations of the single-particle basis on the convergence behavior and robustness of ab initio no-core shell model calculations. Our focus is on novel basis sets defined by the natural orbitals of a correlated…

Nuclear Theory · Physics 2019-03-27 Alexander Tichai , Julius Müller , Klaus Vobig , Robert Roth

We extend to strongly correlated molecular systems the recently introduced basis-set incompleteness correction based on density-functional theory (DFT) [E. Giner et al., J. Chem. Phys. 149, 194301 (2018)]. This basis-set correction relies…

Chemical Physics · Physics 2020-05-20 Emmanuel Giner , Anthony Scemama , Pierre-François Loos , Julien Toulouse

We describe a simple scheme to construct a low-energy effective Hamiltonian H_eff for highly correlated systems containing non-metals like O, P or As (O in what follows) and a transition-metal (M) as the active part in the electronic…

Strongly Correlated Electrons · Physics 2015-05-18 A. A. Aligia , T. Kroll

The structure of approximate two electron wavefunction is deeply investigated, both theoretically and numerically, in the strong-field driven ionization dynamics. Theoretical analyses clarify that for two electron singlet systems, the…

Atomic Physics · Physics 2014-11-13 Takeshi Sato , Kenichi L Ishikawa

Double hybrid (DH) density functionals are amongst the most accurate density functional approximations developed so far, largely due to incorporation of correlation effects from unoccupied orbitals via second order perturbation theory…

Chemical Physics · Physics 2018-05-07 Diptarka Hait , Martin Head-Gordon

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

Orbital-free density functional theory (OF-DFT) runs at low computational cost that scales linearly with the number of simulated atoms, making it suitable for large-scale material simulations. It is generally considered that OF-DFT strictly…

Materials Science · Physics 2022-04-05 Qiang Xu , Cheng Ma , Wenhui Mi , Yanchao Wang , Yanming Ma

In this work, we extend the Piris natural orbital functionals (PNOFs) to excited states by coupling their reconstructed second-order reduced density matrices with the extended random-phase approximation (ERPA). We have named the general…

Multi-configurational approaches yield universal wave function parameterizations that can qualitatively well describe electronic structures along reaction pathways. For quantitative results, multi-reference perturbation theory is required…

Chemical Physics · Physics 2016-09-08 Christopher J. Stein , Vera von Burg , Markus Reiher

Hybrid functionals' non-local exchange-correlation potential contains a derivative discontinuity that improves on standard semi-local density functional theory (DFT) band gaps. Moreover, by careful parameterization, hybrid functionals can…

Materials Science · Physics 2017-11-06 Viktor Ivády , Adam Gali , Igor A. Abrikosov

Multireference effects are associated with degeneracies and near-degeneracies of the ground state and are critical to a variety of systems. Most approximate functionals of density functional theory (DFT) fail to properly describe these…

Quantum Physics · Physics 2021-09-17 Conrad Lewis , Emil Proynov , Jianguo Yu , Jing Kong

We present a novel route to constructing cost-efficient semi-empirical approximations for the non-additive kinetic energy in subsystem density functional theory. The developed methodology is based on the use of Slater determinants composed…

Chemical Physics · Physics 2025-01-13 Larissa Sophie Eitelhuber , Denis G. Artiukhin

In this work, the required algebra to employ the resolution of the identity approximation within Piris Natural Orbital Functional (PNOF) is developed, leading to an implementation named DoNOF-RI. The arithmetic scaling is reduced from…

Chemical Physics · Physics 2023-01-05 Juan Felipe Huan Lew-Yee , Mario Piris , Jorge M. del Campo

This work presents a novel approach to distribute orbitals into subspaces within electron-pairing-based natural orbital functionals (NOFs). This approach modifies the coupling between weakly and strongly occupied orbitals by applying an…

Chemical Physics · Physics 2025-02-05 Élodie Boutou , Juan Felipe Huan Lew-Yee , Jose Maria Mercero , Mario Piris

In this paper, we investigate how nonlocal correlations affect, selectively, the physics of correlated electrons over different energy scales, from the Fermi level to the band-edges. This goal is achieved by applying a diagrammatic…

Strongly Correlated Electrons · Physics 2016-10-24 G. Rohringer , A. Toschi

Electronic correlations could have significant impact on the material properties. They are typically pronounced for localized orbitals and enhanced in low-dimensional systems, so two-dimensional (2D) transition metal compounds could be a…

Materials Science · Physics 2021-09-01 Si Li , Qianqian Wang , Chunmei Zhang , Ping Guo , Shengyuan A. Yang

In the density functional (DF) theory of Kohn and Sham, the kinetic energy of the ground state of a system of noninteracting electrons in a general external field is calculated using a set of orbitals. Orbital free methods attempt to…

Strongly Correlated Electrons · Physics 2009-11-13 Jeng-Da Chai , John D Weeks

This manuscript develops a novel understanding of non-polar solutions of the discrete Painlev\'e I equation (dP1). As the non-autonomous counterpart of an analytically completely integrable difference equation, this system is endowed with a…

Dynamical Systems · Mathematics 2022-10-04 Nicholas Ercolani , Joceline Lega , Brandon Tippings

Evolution of composite spin-orbital order and coupled spin-orbital excitations is studied in a variety of $d^4$ systems with $n$=$4$ electrons in the $t_{2g}$ orbital sector using the generalised self-consistent + fluctuations approach for…

Strongly Correlated Electrons · Physics 2025-04-30 Shahid Ahmad , Harshvardhan Parmar , Shubhajyoti Mohapatra , Avinash Singh

Kohn-Sham density functional theory (DFT) has long struggled with the accurate description of strongly correlated and open shell systems and improvements have been minor even in the newest hybrid functionals. In this Letter we treat the…

Chemical Physics · Physics 2021-04-01 Danny Gibney , Jan-Niklas Boyn , David A. Mazziotti