EuNi5InH1.5−x (x = 0–1.5): hydrogen induced structural and magnetic transitions

Abstract

The new quaternary hydride EuNi₅InH_1.5 has been obtained by hydrogenation of the intermetallic parent EuNi₅In under extremely mild conditions, hence, at room temperature and low hydrogen pressure. Hydrogenation at slightly elevated temperatures and pressures allows for the growth of large crystals, which is a rare observation for intermetallic hydrides. EuNi₅InH_1.5 crystallizes in its own structure type (hP17, Pm2, a = 4.9437(6), c = 10.643(1) Å) with a unique arrangement of the intermetallic host. The hydrogen atoms prefer Ni-surrounded positions, occupying {EuNi₃} and {Eu₂Ni₂} tetrahedral voids in the structure. Upon hydrogenation of EuNi₅In an anisotropic volume expansion accompanied with a decrease of symmetry is observed. Magnetic measurements reveal antiferromagnetic ordering in the hydride below 4 K and indicate an intermediate +II/+III oxidation state for Eu both in the intermetallic phase and the hydride. X-ray photoemission spectroscopy confirms the existence of the two different oxidation states of Eu. The hydrogenation does not affect the oxidation state of Eu and the type of magnetic ordering, but exerts a strong influence on the transition temperature, crystal structure, mechanical and electrical properties. Crystallographic analysis suggests that Eu(II) and Eu(III) do not order but rather mix homogeneously on crystallographic sites. Electronic structure calculations reveal the metallic character of the hydride with several different types of chemical bonding interactions being present in the compound ranging from the formally ionic Eu–H to covalent Ni–H and delocalized metal–metal. Geometry optimization confirm the thermodynamic instability of the intermetallic host lattice for the hydride and supports a transformation into the parental structure as observed experimentally.