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Local electronic-structure methods in quantum chemistry operate on the ability to compress electron correlations more efficiently in a basis of spatially localized molecular orbitals than in a parent set of canonical orbitals. However, many…

Chemical Physics · Physics 2024-08-01 Jonas Greiner , Jürgen Gauss , Janus J. Eriksen

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

We present a new linear scaling method for the energy minimization step of semiempirical and first-principles Hartree-Fock and Kohn-Sham calculations. It is based on the self-consistent calculation of the optimum localized orbitals of any…

Materials Science · Physics 2009-11-10 Luis Seijo , Zoila Barandiaran

We introduce an efficient method to construct optimal and system adaptive basis sets for use in electronic structure and quantum Monte Carlo calculations. The method is based on an embedding scheme in which a reference atom is singled out…

Strongly Correlated Electrons · Physics 2016-02-02 Sandro Sorella , Nicolas Devaux , Mario Dagrada , Guglielmo Mazzola , Michele Casula

Attaining a reliable complete basis set (CBS) limit remains a significant challenge in ab initio correlated electronic-structure calculations. Building on our previous work for atoms and diatomic molecules, we present a finite-element (FE)…

Materials Science · Physics 2026-03-30 Hao Peng , Haochen Liu , Chuhao Li , Hehu Xie , Xinguo Ren

The recently developed localized orbital scaling correction (LOSC) method shows the ability to systematically and size-consistently reduce the delocalization error existing in conventional density functional approximations (DFAs). Applying…

Chemical Physics · Physics 2020-10-19 Yuncai Mei , Zehua Chen , Weitao Yang

Basis sets of atomic orbitals are very efficient for density functional calculations but lack a systematic variational convergence. We present a variational method to optimize numerical atomic orbitals using a single parameter to control…

Condensed Matter · Physics 2009-11-07 E. Anglada , J. Soler , J. Junquera , E. Artacho

The implementation of the orbital minimization method (OMM) for solving the self-consistent Kohn-Sham (KS) problem for electronic structure calculations in a basis of non-orthogonal numerical atomic orbitals of finite-range is reported. We…

Computational Physics · Physics 2014-02-06 Fabiano Corsetti

An ab initio approach formulated under an entropy-inspired repartitioning of the electronic Hamiltonian is presented. This ansatz produces orbital eigenvalues each shifted by entropic contributions expressed as subsets of scaled pair…

Chemical Physics · Physics 2025-06-10 Abdulrahman Y. Zamani , Kevin Carter-Fenk

The model of continuous spontaneous localization (CSL) is the most prominent consistent modification of quantum mechanics predicting an objective quantum-to-classical transition. Here we show that precision interferometry with Bose-Einstein…

It has been well established that the Jastrow correlation factor can effectively capture the electron correlation effects, and thus, the efficient optimization of the many-body wave function including the Jastrow correlation factor is of…

Atomic Physics · Physics 2023-09-12 Masayuki Ochi

A simple scheme is described for introducing the correct cusps at nuclei into orbitals obtained from Gaussian basis set electronic structure calculations. The scheme is tested with all-electron variational quantum Monte Carlo (VMC) and…

Computational Physics · Physics 2008-01-18 A. Ma , M. D. Towler , N. D. Drummond , R. J. Needs

A widely used strategy to reduce the computational cost in quantum-chemical calculations is to partition the system into an active subsystem, which is the focus of the computational efforts and an environment that is treated at a lower…

Chemical Physics · Physics 2023-06-19 Elena Kolodzeiski , Christopher J. Stein

We propose a unique scheme to construct fully optimized atomic basis sets for density-functional calculations. The shapes of the radial functions are optimized by minimizing the {\it spillage} of the wave functions between the atomic…

Materials Science · Physics 2015-05-19 Mohan Chen , G-C Guo , Lixin He

A quantum Monte Carlo method of determining Jastrow-Slater wave functions for which the energy is stationary with respect to variations in the single-particle orbitals is presented. A potential is determined by a least-squares fitting of…

Condensed Matter · Physics 2007-05-23 Stephen Fahy , Claudia Filippi

We present a basis set correction scheme for the coupled-cluster singles and doubles (CCSD) method. The scheme is based on employing frozen natural orbitals (FNOs) and diagrammatically decomposed contributions to the electronic correlation…

Materials Science · Physics 2021-06-18 Andreas Irmler , Alejandro Gallo , Andreas Grüneis

We describe a method for imposing the correct electron-nucleus (e-n) cusp in molecular orbitals expanded as a linear combination of (cuspless) Gaussian basis functions. Enforcing the e-n cusp in trial wave functions is an important asset in…

Chemical Physics · Physics 2020-06-05 Pierre-François Loos , Anthony Scemama , Michel Caffarel

All-electron Fixed-node Diffusion Monte Carlo (FN-DMC) calculations for the nonrelativistic ground-state energy of the water molecule at equilibrium geometry are presented. The determinantal part of the trial wavefunction is obtained from a…

Chemical Physics · Physics 2016-05-25 Michel Caffarel , Thomas Applencourt , Emmanuel Giner , Anthony Scemama

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

Quantum chemistry calculations are often performed using atom-centered basis sets which are chosen to balance accuracy and cost. While they are systematically improvable, the total energy converges slowly with basis set size towards the…

Chemical Physics · Physics 2026-05-18 Nicolas Grimblat , Gabriel Klassen , Guido Falk von Rudorff
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