Pressure-stabilized hexafluorides of first-row transition metals

Fluorine chemistry was demonstrated to show the importance of stretching the limits of chemical synthesis, oxidation state, and chemical bonding at ambient conditions. Thus far, the highest fluorine stoichiometry of a neutral first-row transition-metal fluoride is five, in VF and CrF . Pressure can...

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Bibliographic Details
Published in:Physical chemistry chemical physics : PCCP 2022-01, Vol.24 (3), p.1736-1742
Main Authors: Lin, Jianyan, Yang, Qiuping, Li, Xing, Zhang, Xiaohua, Li, Fei, Yang, Guochun
Format: Article
Language:English
Subjects:
Chemical bonds
Chemical synthesis
First principles
Fluorination
Fluorine
Metal fluorides
Metals
Oxidation
Stoichiometry
Transition metals
Valence
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Summary:Fluorine chemistry was demonstrated to show the importance of stretching the limits of chemical synthesis, oxidation state, and chemical bonding at ambient conditions. Thus far, the highest fluorine stoichiometry of a neutral first-row transition-metal fluoride is five, in VF and CrF . Pressure can stabilize new stoichiometric compounds that are inaccessible at ambient conditions. Here, we attempted to delineate the fluorination limits of first-row transition metals at a high pressure through first-principles swarm-intelligence structure searching simulations. Besides reproducing the known compounds, our extensive search has resulted in a plethora of unreported compounds: CrF , MnF , FeF , FeF , FeF , and CoF , indicating that the application of pressure achieves not only the fluorination limit ( , hexafluoride) but also the long-sought bulky tetrafluorides. Our current results provide a significant step forward towards a comprehensive understanding of the fluorination limit of first-row transition metals.
ISSN:1463-9076
1463-9084
DOI:10.1039/d1cp04446j