Electronegativity and chemical hardness of the elements under pressure

TL;DR

This paper investigates how electronegativity and chemical hardness of elements change under pressure, revealing trends and orbital transfers that explain exotic chemical phenomena and metallization.

Contribution

It introduces pressure-dependent models for electronegativity and chemical hardness, providing new insights into atomic behavior and chemical rules under high-pressure conditions.

Findings

Electronegativity and hardness generally decrease with pressure.

Pressure induces s-d orbital transfer in transition metals.

Some elements become pseudo-noble-gas or highly electropositive under pressure.

Abstract

Abundant evidence has shown the emergence of exotic chemical phenomena under pressure, including the formation of unexpected compounds and strange crystal structures. In many cases, there is no convincing explanation for these phenomena and there are virtually no chemical rules or models capable of predicting or even rationalizing these phenomena. Here we calculate, as a function of pressure, two central chemical properties of atoms, electronegativity and chemical hardness, which can be seen as the first and second-order chemical potentials. Mulliken electronegativity, which equals minus the chemical potential of the electron relative to the vacuum, is appropriately modified - instead of taking the vacuum (impossible under high pressure), we take the homogeneous electron gas as reference. We find that for most elements, chemical hardness and electronegativity decrease with pressure, consistent with pressure-induced metallization. Furthermore, we discover that pressure-induced s-d orbital transfer makes Ni, Pd and Pt "pseudo-noble-gas" atoms with a closed d-shell configuration, and the elements preceding them (Fe and especially Co, Rh, Ir) electron acceptors, while the elements right after them (Cu, Ag, Zn, Cd, for example) become highly electropositive. We show the explicative and predictive power of our electronegativity and chemical hardness scales under pressure.