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

Autor(en)

Giorgio Domenichini

Abstrakt

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(en)

Computergestützte Materialphysik

Journal

Journal of Chemical Physics

Band

160

Anzahl der Seiten

7

ISSN

0021-9606

DOI

https://doi.org/10.1063/5.0196383

Publikationsdatum

03-2024

Peer-reviewed

Ja

ÖFOS 2012

104022 Theoretische Chemie

ASJC Scopus Sachgebiete

Allgemeine Physik und Astronomie, Physical and Theoretical Chemistry

Link zum Portal

https://ucrisportal.univie.ac.at/de/publications/a9b46316-753e-49fb-82f0-a7ca1754b917