Original scientific paper

https://doi.org/10.5562/cca3817

Decomposition of Molecular Integrals into Atomic Contributions via Becke Partitioning Scheme: a Caveat

Francesco F. Summa orcid.org/0000-0001-7573-7136 ; Department of Chemistry and Biology, University of Salerno, via Giovanni Paolo II 132, 84084, Fisciano (SA), Italy
Guglielmo Monaco ; Department of Chemistry and Biology, University of Salerno, via Giovanni Paolo II 132, 84084, Fisciano (SA), Italy
Riccardo Zanasi orcid.org/0000-0002-8374-6080 ; Department of Chemistry and Biology, University of Salerno, via Giovanni Paolo II 132, 84084, Fisciano (SA), Italy

Abstract

Decomposition of molecular integrals into physically meaningful atomic contributions by means of the Becke integration scheme requires some care with respect to the choice of suitable atomic size adjustments. Using a simple illustrative example, it is shown that the adjustment of cell boundaries, as originally proposed by considering Bragg-Slater atomic radii, does not provide reliable results. Alternatively, the positions of the bond critical points of the electron density can be adopted to define heteronuclear cutoff profiles which allow for a more reasonable atomic partition of the molecular electron density.

This work is licensed under a Creative Commons Attribution 4.0 International License.

Keywords

molecular integrals; atomic contributions; density functions; bond critical points; charge transfer

Hrčak ID:

265152

URI

https://hrcak.srce.hr/265152

Publication date:

28.6.2021.

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