Extending the definition of atomic basis sets to atoms with fractional nuclear charge

Giorgio Domenichini

doi:10.1063/5.0196383

Title

Extending the definition of atomic basis sets to atoms with fractional nuclear charge

Author

Giorgio Domenichini

Faculty of Physics, University of Vienna

Abstract

Alchemical transformations showed that perturbation theory can be applied also to changes in the atomic nuclear charges of a molecule. The alchemical path that connects two different chemical species involves the conceptualization of a non-physical system in which an atom possess a non-integer nuclear charge. A correct quantum mechanical treatment of these systems is limited by the fact that finite size atomic basis sets do not define exponents and contraction coefficients for fractional charge atoms. This paper proposes a solution to this problem and shows that a smooth interpolation of the atomic orbital coefficients and exponents across the periodic table is a convenient way to produce accurate alchemical predictions, even using small size basis sets.

Keywords

Density functional theoryChemical spaceBasis setsFukui functionMachine learningPerturbation theoryDiatomic moleculeChemical physicsCatalysts and CatalysisStatistical thermodynamics

Object type

journal article

Language

English [eng]

Persistent identifier

https://phaidra.univie.ac.at/o:2084748

DOI

10.1063/5.0196383

Appeared in

Title

The Journal of Chemical Physics

Volume