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The performance of basis sets made of numerical atomic orbitals is explored in density-functional calculations of solids and molecules. With the aim of optimizing basis quality while maintaining strict localization of the orbitals, as…

Materials Science · Physics 2009-11-07 Javier Junquera , Oscar Paz , Daniel Sanchez-Portal , Emilio Artacho

The intersection of Quantum Chemistry and Quantum Computing has led to significant advancements in understanding the potential of using quantum devices for the efficient calculation of molecular energies. Simultaneously, this intersection…

Quantum Physics · Physics 2025-09-03 Davide Materia , Leonardo Ratini , Celestino Angeli , Leonardo Guidoni

The simultaneous treatment of static and dynamical correlations in strongly-correlated electron systems is a critical challenge. In particular, finding a universal scheme for identifying a single-particle orbital basis that minimizes the…

Quantum Physics · Physics 2024-08-07 Ke Liao , Lexin Ding , Christian Schilling

Occupation numbers of natural orbitals capture the physics of strong electron correlations in momentum space. A Natural Orbital Density Functional Theory based on the antisymmetrized geminal product provides these occupation numbers and the…

Strongly Correlated Electrons · Physics 2014-05-06 B. Barbiellini

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

The current work presents a natural orbital functional (NOF) for electronic systems with any spin value independent of the external potential being considered, that is, a global NOF (GNOF). It is based on a new two-index reconstruction of…

Chemical Physics · Physics 2021-12-07 Mario Piris

Through ab initio approaches in nuclear theory, we may now seek to quantitatively understand the wealth of nuclear collective phenomena starting from the underlying internucleon interactions. No-core configuration interaction (NCCI)…

Nuclear Theory · Physics 2015-11-09 M. A. Caprio , P. Maris , J. P. Vary , R. Smith

We investigate whether the natural orbitals (NOs) minimize $\lVert\Psi - \Phi\rVert^2$, where $\Psi$ is a wave function and $\Phi$ is a full configuration interaction (CI) approximation to $\Psi$ in a truncated basis. We will show that the…

Quantum Physics · Physics 2013-12-11 Klaas J. H. Giesbertz

The analytic energy gradients with respect to nuclear motion are derived for natural orbital functional (NOF) theory. The resulting equations do not require to resort to linear-response theory, so the computation of NOF energy gradients is…

Chemical Physics · Physics 2017-09-13 Ion Mitxelena , Mario Piris

An energy functional for orbital based $O(N)$ calculations is proposed, which depends on a number of non orthogonal, localized orbitals larger than the number of occupied states in the system, and on a parameter, the electronic chemical…

mtrl-th · Physics 2016-09-07 Jeongnim Kim , Francesco Mauri , Giulia Galli

We introduce a method for accurate quantum chemical calculations based on a simple variational wave function, defined by a single geminal that couples all the electrons into singlet pairs, combined with a real space correlation factor. The…

Materials Science · Physics 2009-10-22 M. Marchi , S. Azadi , M. Casula , S. Sorella

In the present letter, it is demonstrated how full configuration interaction (FCI) results in extended basis sets may be obtained to within sub-kJ/mol accuracy by decomposing the energy in terms of many-body expansions in the virtual…

Chemical Physics · Physics 2017-09-15 Janus J. Eriksen , Filippo Lipparini , Jürgen Gauss

The emergence of rotational bands is observed in no-core configuration interaction (NCCI) calculations for the odd-mass Be isotopes (7<=A<=13) with the JISP16 nucleon-nucleon interaction, as evidenced by rotational patterns for excitation…

Nuclear Theory · Physics 2014-09-02 M. A. Caprio , P. Maris , J. P. Vary

Calculations in ab initio no-core configuration interaction (NCCI) approaches, such as the no-core shell model or no-core full configuration methods, have conventionally been carried out using the harmonic-oscillator many-body basis.…

Nuclear Theory · Physics 2013-01-08 M. A. Caprio , P. Maris , J. P. Vary

The cost of simulating quantum many-body systems - on classical or quantum hardware - scales with the number of variational parameters, so progress at fixed computational budget hinges on more parameter-efficient ans\"atze. Configuration…

Quantum Physics · Physics 2026-05-25 Hao Zhang , Matthew Otten

The projection of the eigenfunctions obtained in standard plane-wave first-principle electronic-structure calculations into atomic-orbital basis sets is proposed as a formal and practical link between the methods based on plane waves and…

Condensed Matter · Physics 2009-10-28 Daniel Sanchez-Portal , Emilio Artacho , Jose M. Soler

Molecule-optimized basis sets, based on approximate natural orbitals, are developed for accelerating the convergence of quantum calculations with strongly correlated (multi-referenced) electrons. We use a low-cost approximate solution of…

Chemical Physics · Physics 2014-02-12 Gergely Gidofalvi , David A. Mazziotti

Modern quantum chemistry can make quantitative predictions on an immense array of chemical systems. However, the interpretation of those predictions is often complicated by the complex wave function expansions used. Here we show that an…

Chemical Physics · Physics 2013-11-12 Gerald Knizia

The natural orbitals and natural occupation numbers of various N = Z, sp and sd shell nuclei are calculated by applying a correlated one-body density matrix. The correlated density matrix has been evaluated by considering central…

Nuclear Theory · Physics 2013-08-21 V. P. Psonis , Ch. C. Moustakidis , S. E. Massen

We introduce natural atomic orbitals as the local projector to define the correlated subspace for DFT + DMFT (density functional theory plus dynamical mean-field theory) calculation. The natural atomic orbitals are found to be stably…

Strongly Correlated Electrons · Physics 2020-01-01 Jae-Hoon Sim , Myung Joon Han