Potential rules for stable transition metal hexafluorides with high oxidation states under high pressures

Abstract

High pressure is a powerful tool in material sciences which can lead to the discovery of novel inorganic species in high oxidation states. Based on the prediction of the stability of PdF₆ with a high Pd oxidation state of +6, we propose three potential guiding rules for finding stable transition metal (TM) fluorides with high +6 oxidation states: (1) the existence of a large (>7 eV) valence orbitals energy differences of atoms between the TM d orbital and the F 2p orbital; (2) an appropriate number of valence electrons within the range of 6–11; and (3) suitable electronegativity values less than 2.3 on the Pauli scale. More importantly, by synergistically invoking all of these rules, we predict, by combining a particle swarm optimization algorithm with first-principles calculation on the phase stabilities of the various TM–F compounds, a collection of new TMF₆ species with the space group Pnma that have a +6 oxidation state. Subsequently, we develop an understanding of the high +6 oxidation state for the TM elements. These findings are expected to play a crucial role in the predictive discoveries of new fluorides with high oxidation states of +6.