Potential rules for stable transition metal hexafluorides with high oxidation states under high pressures. Issue 9 (21st February 2023)

• Record Type: Journal Article
• Authors: Ma, Shiyin; Zhao, Liang; Li, Shichang; Gao, Tao; Peng, Feng
• Is Part Of: Physical chemistry chemical physics. Volume 25:Issue 9(2023)
• Page Start: 6726
• Page End: 6732
• Publication Date: 2023-02-21
• Subjects: Chemistry, Physical and theoretical -- Periodicals; 541.3
• DOI: 10.1039/d2cp05418c
• Languages: English
• ISSNs: 1463-9076

Abstract

Abstract : Three potential guiding rules to explore the stability and the high oxidation state with +6 in Transition Metal (TM) fluorides have been proposed. A collection of new TMF6 with space group Pnma, showing +6 oxidation state have been predicted. 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.