najoNanosystems: Physics, Chemistry, MathematicsНаносистемы: физика, химия, математика2220-80542305-7971Университет ИТМО10.17586/22208054201785677687najo-741Research ArticleCHEMISTRY AND MATERIALS SCIENCEХИМИЯ И НАУКА О МАТЕРИАЛАХUniversal mechanism of tetrahedral metal cluster formation in structures with breathing pyrochlore sublatticesTalanovM. V.

RostovonDon

tmikleman@mail.ruTalanoV. M.

Novocherkassk

valtalanov@mail.ruResearch Institute of Physics, Southern Federal UniversityRussian FederationSouthRussian State Polytechnical UniversityRussian Federation20171208202585677687Copyright © Talanov M.V., Talano V.M., 20252025Talanov M.V., Talano V.M.Talanov M.V., Talano V.M.Данная работа распространяется под лицензией Creative Commons Attribution 4.0.This work is licensed under a Creative Commons Attribution 4.0 License.https://nanojournal.ifmo.ru/jour/article/view/741

A universal mechanism of tetrahedral metal cluster formation in crystal with geometrically frustrated pyrochlore sublattices is pr oposed. It has been shown that the critical irreducible representation , which generated the formation of metal clusters in noncentrosymmetrical F4 3mphases from high symmetry phases with Fd3 m space group, is a one dimensional irreducible representation 11(4(A2u)) (in Kovalev notation). The structural theory of metal cluster formation based on group theoretical calculations was published earlier for the case of Aordered spinel. In this work, the theory is generalized in the case of any high symmetry Fd3 m structures that include pyrochlore sublattices. We presented a brief review of such structures and mechanisms of the tetrahedral metal cluster formation. The existence of so called “breathing” pyrochlore sublattices in ordered phases is predicted theoretically. The groups of atoms, between which bond clusters, are found. These groups of atoms define electron correlation effects. Examples of tetrahedral metal cluster formation in ordered spinels, ordered lacunar spinels, ordered Laves phases (MgCu4Sn structural type) and ordered pyrochlore are considered. The theoretical results are confirmed by the known experimental facts.

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The authors declare that there are no conflicts of interest present.