Quantum Alchemy Based Bonding Trends and Their Link to Hammett’s Equation and Pauling’s Electronegativity Model

Autor(en)

Michael J. Sahre, Guido Falk von Rudorff, O. Anatole von Lilienfeld

Abstrakt

We present an intuitive and general analytical approximation estimating the energy of covalent single and double bonds between participating atoms in terms of their respective nuclear charges with just three parameters, [EAB ≈ a - bZAZB + c(ZA7/3 + ZB7/3) ]. The functional form of our expression models an alchemical atomic energy decomposition between participating atoms A and B. After calibration, reasonably accurate bond dissociation energy estimates are obtained for hydrogen-saturated diatomics composed of p-block elements coming from the same row 2 ≤ n ≤ 4 in the periodic table. Corresponding changes in bond dissociation energies due to substitution of atom B by C can be obtained via simple formulas. While being of different functional form and origin, our model is as simple and accurate as Pauling’s well-known electronegativity model. Analysis indicates that the model’s response in covalent bonding to variation in nuclear charge is near-linear, which is consistent with Hammett’s equation.

Organisation(en)

Computergestützte Materialphysik

Externe Organisation(en)

Universität Kassel, Vector Institute for Artificial Intelligence, University of Toronto, Technische Universität Berlin

Journal

Journal of the American Chemical Society

Band

145

Seiten

5899-5908

Anzahl der Seiten

10

ISSN

0002-7863

DOI

https://doi.org/10.1021/jacs.2c13393

Publikationsdatum

03-2023

Peer-reviewed

Ja

ÖFOS 2012

103018 Materialphysik, 104017 Physikalische Chemie

ASJC Scopus Sachgebiete

Catalysis, Allgemeine Chemie, Biochemistry, Colloid and Surface Chemistry

Link zum Portal

https://ucrisportal.univie.ac.at/de/publications/47f791ee-ccc4-4093-9de5-aadcc9b82577