New intergrowth compounds in the La–Co–Al system, La3Co5Al2, La6Co7Al7, and La4Co9.6Al3.4: Crystal structures, bonding, and magnetism

Chernyshev, I.V.; Tursina, A.I.; Nesterenko, S.N.; Strydom, A.M.; Kuznetsov, A.N.

Авторы: Chernyshev Ilja V., Tursina Anna I., Nesterenko Sergey N., Strydom André M., Kuznetsov Alexey N.
Журнал: Journal of Solid State Chemistry
Том: 344
Год издания: 2025
Издательство: Elsevier B.V.
Местоположение издательства: Netherlands
Номер статьи: 125177
DOI: 10.1016/j.jssc.2024.125177
Аннотация: Three new intergrowth compounds in the La–Co–Al system have been synthesized using arc-melting with subsequent annealing. La3Co5Al2 and La6Co7Al7 crystallize in the La6Co11Ga3-type (I4/mcm, tI80) with stoichiometry defined by different filling of the two Co sites: a = 8.1959 (8), c = 23.082 (7) Å (La3Co5Al2) and a = 8.2426 (13), c = 23.768 (10) Å (La6Co7Al7). The structures present a stacking variant of the YNi9In2-, U3Si2-, and CuAl2-type layers along the c-direction. La4Co9.6Al3.4 compound crystallizes with its own type (P4/mbm, tP34, a = 8.2060 (13), c = 8.989 (2) Å) and represents an intergrowth structure composed of YNi9In2- and U3Si2-type slabs stacked along the c-axis. La3Co5Al2 and La6Co7Al7 compounds do not form a homogeneous region whereas for La4Co9.6Al3.4 compound a narrow solid solubility range has been detected. DFT calculations predict all compounds to be metallic, with Co d-states playing a major role near the Fermi level. Bonding analysis reveals a large number of bonding contacts for each compound and indicates complex systems of delocalized bonding. Combined specific heat and magnetic susceptibility measurement data indicate low-temperature transition to a magnetic state for the La4Co9.6Al3.4 compound.
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New intergrowth compounds in the La–Co–Al system, La3Co5Al2, La6Co7Al7, and La4Co9.6Al3.4: Crystal structures, bonding, and magnetismстатья

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