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

Author(s)
Giorgio Domenichini
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.

Organisation(s)
Computational Materials Physics
Journal
Journal of Chemical Physics
Volume
160
No. of pages
7
ISSN
0021-9606
DOI
https://doi.org/10.1063/5.0196383
Publication date
03-2024
Peer reviewed
Yes
Austrian Fields of Science 2012
104022 Theoretical chemistry
ASJC Scopus subject areas
General Physics and Astronomy, Physical and Theoretical Chemistry
Portal url
https://ucrisportal.univie.ac.at/en/publications/a9b46316-753e-49fb-82f0-a7ca1754b917