Abstract
The electronegativity concept was first formulated by Pauling in the first half of the 20th century to explain quantitatively the properties of chemical bonds between different types of atoms. Today, it is widely known that, in high-pressure regimes, the reactivity properties of atoms can change, and, thus, the bond patterns in molecules and solids are affected. In this work, we studied the effects of high pressure modeled by a confining potential on different definitions of electronegativity and, additionally, tested the accuracy of first-order perturbation theory in the context of density functional theory for confined atoms of the second row at the Hartree–Fock level. As expected, the electronegativity of atoms at high confinement is very different than that of their free counterparts since it depends on the electronic configuration of the atom, and, thus, its periodicity is modified at higher pressures.
Highlights
Electronegativity is one of the most important empirical concepts in chemistry, and the study of its variations in extreme conditions could be of importance
In this work, we first discuss some of the most important equations to calculate electronegativity, always keeping in mind that it is an empirical concept and so it is impossible to derive it from the laws of quantum mechanics
All calculations were done at the Hartree–Fock level since in a previous work we demonstrated that the orbital energies are well represented at this level of theory [18]
Summary
Electronegativity is one of the most important empirical concepts in chemistry, and the study of its variations in extreme conditions could be of importance. In this work, we first discuss some of the most important equations to calculate electronegativity, always keeping in mind that it is an empirical concept and so it is impossible to derive it from the laws of quantum mechanics. The other point treated in this work is confinement, which can change the electronic structure of the atom. It can affect its reactivity and its possible catalytic properties, and, in solids, it can change, for instance, the crystallographic phase and induce superconductivity. We show the different forms to do the confinement, which can use rigid walls or soft walls. It can be simulated using a cavity inside a dielectric medium. We discuss our results for the atoms from hydrogen to neon
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