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We describe an accurate and scalable implementation for the computation of molecular nuclear magnetic resonance shieldings, J-couplings, and magnetizabilities within nonrelativistic semilocal density functional theory, based on numeric…

Computational Physics · Physics 2020-02-25 Raul Laasner , William Huhn , Johannes Colell , Thomas Theis , Victor Yu , Warren Warren , Volker Blum

The random phase approximation (RPA) as formulated as an orbital-dependent, fifth-rung functional within the density functional theory (DFT) framework offers a promising approach for calculating the ground-state energies and the derived…

Computational Physics · Physics 2023-07-25 Rong Shi , Peize Lin , Min-Ye Zhang , Lixin He , Xinguo Ren

Large atomic-orbital (AO) basis sets of at least triple and preferably quadruple-zeta (QZ) size are required to adequately converge Kohn-Sham density functional theory (DFT) calculations towards the complete basis set limit. However,…

Chemical Physics · Physics 2025-12-02 Anthony O. Lara , Justin J. Talbot , Zhe Wang , Martin Head-Gordon

We propose large-core correlation-consistent pseudopotential basis sets for the heavy p-block elements Ga-Kr and In-Xe. The basis sets are of cc-pVTZ and cc-pVQZ quality, and have been optimized for use with the large-core…

Chemical Physics · Physics 2009-11-06 Jan M. L. Martin , Andreas Sundermann

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

LibRPA is a software package designed for efficient calculations of random phase approximation (RPA) electron correlation energies from first principles using numerical atomic orbital (NAOs). Leveraging a localized resolution of identity…

Materials Science · Physics 2024-07-30 Rong Shi , Min-Ye Zhang , Peize Lin , Lixin He , Xinguo Ren

In wavefunction-based $\textit{ab-initio}$ quantum mechanical calculations, achieving absolute convergence with respect to the one-electron basis set is a long-standing challenge. In this work, using the random phase approximation (RPA)…

Materials Science · Physics 2025-10-17 Hao Peng , Xinguo Ren

Core-valence basis sets for the alkali and alkaline earth metals Li, Be, Na, Mg, K, and Ca are proposed. The basis sets are validated by calculating spectroscopic constants of a variety of diatomic molecules involving these elements.…

Chemical Physics · Physics 2009-11-10 Mark A. Iron , Mikhal Oren , Jan M. L. Martin

To solve the Kohn-Sham equation within the framework of density functional theory, we develop a scheme to construct numerical atomic orbital (NAO) basis sets by contracting truncated spherical waves (TSWs). The contraction minimizes the…

Chemical Physics · Physics 2026-04-10 Yike Huang , Zuxin Jin , Linfeng Zhang , Mohan Chen , Rui Chen , Ling Li

Multicomponent methods are a conceptually simple way to include nuclear quantum effects into quantum chemistry calculations. In multicomponent methods, the electronic molecular orbitals are described using the linear combination of atomic…

Chemical Physics · Physics 2022-12-02 Irina Samsonova , Gabrielle B. Tucker , Naresh Alaal , Kurt R. Brorsen

In the context of high-accuracy computational thermochemistry, the valence CCSD correlation component of molecular atomization energies present the most severe basis set convergence problem, followed by the (T) component. In the present…

Chemical Physics · Physics 2016-06-23 Nitai Sylvetsky , Kirk A. Peterson , Amir Karton , Jan M. L. Martin

The high computational scaling with the number of correlated electrons and the size of the basis set is a bottleneck which limits applications of coupled cluster (CC) algorithms. This is particularly so for calculations based on 2- or…

Chemical Physics · Physics 2022-06-13 Xiang Yuan , Lucas Visscher , Andre Severo Pereira Gomes

Most modern calculations of many-electron atoms use basis sets of atomic orbitals. An accurate account for the electronic correlations in heavy atoms is very difficult computational problem and optimization of the basis sets can reduce…

Atomic Physics · Physics 2024-01-17 M. G. Kozlov , Yu. A. Demidov , M. Y. Kaygorodov , E. V. Triapitsyna

We provide an integration of the universal, perturbative explicitly correlated [2]$_\text{R12}$-correction in the context of the Variational Quantum Eigensolver (VQE). This approach is able to increase the accuracy of the underlying…

Quantum Physics · Physics 2022-07-08 Philipp Schleich , Jakob S. Kottmann , Alán Aspuru-Guzik

We have developed and benchmarked a new extended basis set for explicitly correlated calculations, namely cc-pV5Z-F12. It is offered in two variants, cc-pV5Z-F12 and cc- pV5Z-F12(rev2), the latter of which has additional basis functions on…

Chemical Physics · Physics 2015-07-16 Kirk A. Peterson , Manoj Kumar Kesharwani , Jan M. L. Martin

The Bethe-Salpeter equation (BSE) based on GW quasiparticle levels is a successful approach for calculating the optical gaps and spectra of solids and also for predicting the neutral excitations of small molecules. We here present an…

Materials Science · Physics 2020-02-19 Chi Liu , Jan Kloppenburg , Xinguo Ren , Heiko Appel , Yosuke Kanai , Volker Blum

Explicitly correlated methods such as MP2-F12 and CCSD(F12*) exhibit much faster basis set convergence (asymptotically $\propto L^{-7}$, with L the highest angular momentum) than orbital-only approaches. Yet it has been pointed out that…

Chemical Physics · Physics 2026-05-22 Vladimir Fishman , Jan M. L. Martin

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 finite basis set errors for all-electron random-phase approximation (RPA) correlation energy calculations are analyzed for isolated atomic systems. We show that, within the resolution-of-identity (RI) RPA framework, the major source of…

Chemical Physics · Physics 2023-06-21 Hao Peng , Sixian Yang , Hong Jiang , Hongming Weng , Xinguo Ren

Relativistic basis sets of quintuple-zeta quality are presented for the s-block elements. The basis sets include SCF exponents for the occupied spinors and for the np shell (the latter is considered here a valence orbital). Valence and core…

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