Efficient implementation of the superposition of atomic potentials initial guess for electronic structure calculations in Gaussian basis sets

Susi Lehtola*, Lucas Visscher, Eberhard Engel

*Corresponding author for this work

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Abstract

The superposition of atomic potentials (SAP) approach has recently been shown to be a simple and efficient way to initialize electronic structure calculations [S. Lehtola, J. Chem. Theory Comput. 15, 1593-1604 (2019)]. Here, we study the differences between effective potentials from fully numerical density functional and optimized effective potential calculations for fixed configurations. We find that the differences are small, overall, and choose exchange-only potentials at the local density approximation level of theory computed on top of Hartree-Fock densities as a good compromise. The differences between potentials arising from different atomic configurations are also found to be small at this level of theory. Furthermore, we discuss the efficient Gaussian-basis implementation of SAP via error function fits to fully numerical atomic radial potentials. The guess obtained from the fitted potentials can be easily implemented in any Gaussian-basis quantum chemistry code in terms of two-electron integrals. Fits covering the whole periodic table from H to Og are reported for non-relativistic as well as fully relativistic four-component calculations that have been carried out with fully numerical approaches.

Original languageEnglish
Article number144105
Pages (from-to)1-11
Number of pages11
JournalJournal of Chemical Physics
Volume152
Issue number14
Early online date10 Apr 2020
DOIs
Publication statusPublished - 14 Apr 2020

Funding

This work was supported by the Academy of Finland (Suomen Akatemia) through Project No. 311149. Computational resources provided by CSC – It Center for Science Ltd. (Espoo, Finland) and the Finnish Grid and Cloud Infrastructure (persistent identifier urn:nbn:fi:research-infras-2016072533) are gratefully acknowledged.

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