Work

Plain Capping for Improved Accuracy of Approximate One- and Two-Electron Densities at Two-Particle Coalescence Points

Year: 2024

Type: article

Abstract: The values of the one-electron and intracule densities at two-particle coalescence points that enter the expressions for relativistic corrections to energies of Coulombic systems cannot be efficiently computed with sufficient accuracy from approximate wave functions expressed in terms of cuspless basis functions such as the explicitly correlated Gaussians. A new approach to alleviation of this problem, called plain capping, is proposed. Unlike those offered by the previously published formalisms, such as the expectation value identities and integral transforms, the accuracy improvements effected by the plain capping are attained with negligible computational effort and minimum programming. In the case of the on-top two-electron densities, whose accurate computation is particularly costly, the plain capping constitutes the only viable means of error reduction available at present.

Source: Journal of Chemical Theory and Computation

DOI: 10.1021/acs.jctc.4c00533

Authors: Jerzy Cioslowski, Krzysztof Strasburger

Institutions: University of Szczecin, Max Planck Institute for the Physics of Complex Systems, Wrocław University of Science and Technology

Language: English

Topic: Advanced Chemical Physics Studies

Subfield: Atomic and Molecular Physics, and Optics

Field: Physics and Astronomy

Domain: Physical Sciences

Open Access status: hybrid

Estimated APC paid: $4,500

Funders: Max-Planck-Gesellschaft, Narodowe Centrum Nauki, Max-Planck-Institut für Physik Komplexer Systeme