High pressures make Hg a transition metal in a thermodynamically stable solid

TL;DR

This study predicts that under high pressure, mercury can behave as a transition metal by forming stable HgF4 molecules, challenging traditional views of mercury's chemical properties.

Contribution

The paper demonstrates, through first-principles calculations, that high pressure induces mercury to adopt transition metal characteristics by stabilizing HgF4 molecules.

Findings

Hg can transfer electrons in its outer d shell under high pressure

Stable HgF4 molecules form with a planar geometry

Mercury exhibits transition metal behavior at high pressures

Abstract

The appropriateness of including Hg among the transition metals has been debated for a long time. Although the synthesis of HgF$_{4}$ molecules in gas phase was reported before, the molecules show strong instabilities and dissociate. Therefore, the transition metal propensity of Hg remains an open question. Here, we propose that high pressure provides a controllable method for preparing unusual oxidation states of matter. Using an advanced structure search method based on first-principles electronic structure calculations, we predict that under high pressures, Hg can transfer the electrons in its outmost $d$ shell to F atoms, thereby acting as a transition metal. Oxidation of Hg to the +4 state yielded thermodynamically stable molecular crystals consisting of HgF$_{4}$ planar molecules, a typical geometry for $d^{8}$ metal centers.