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Title: EuNi 5 InH 1.5-x (x = 0–1.5): hydrogen induced structural and magnetic transitions

The new quaternary hydride EuNi 5InH 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. EuNi 5InH 1.5 crystallizes in its own structure type ( hP17, P6¯m2, 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 {EuNi 3} and {Eu 2Ni 2} tetrahedral voids in the structure. Upon hydrogenation of EuNi 5In 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 homogeneouslymore » 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. As a result, 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.« less
Authors:
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Publication Date:
Report Number(s):
IS-J-9214
Journal ID: ISSN 2050-7526; JMCCCX
Grant/Contract Number:
AC02-07CH11358
Type:
Accepted Manuscript
Journal Name:
Journal of Materials Chemistry. C
Additional Journal Information:
Journal Volume: 5; Journal Issue: 12; Journal ID: ISSN 2050-7526
Publisher:
Royal Society of Chemistry
Research Org:
Ames Laboratory (AMES), Ames, IA (United States)
Sponsoring Org:
USDOE
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
OSTI Identifier:
1347394

Bigun, Inna, Smetana, Volodymyr, Mudryk, Yaroslav, Hlova, Ihor, Dzevenko, Mariya, Havela, Ladislav, Kalychak, Yaroslav, Pecharsky, Vitalij, and Mudring, Anja-Verena. EuNi 5 InH 1.5-x (x = 0–1.5): hydrogen induced structural and magnetic transitions. United States: N. p., Web. doi:10.1039/c7tc00121e.
Bigun, Inna, Smetana, Volodymyr, Mudryk, Yaroslav, Hlova, Ihor, Dzevenko, Mariya, Havela, Ladislav, Kalychak, Yaroslav, Pecharsky, Vitalij, & Mudring, Anja-Verena. EuNi 5 InH 1.5-x (x = 0–1.5): hydrogen induced structural and magnetic transitions. United States. doi:10.1039/c7tc00121e.
Bigun, Inna, Smetana, Volodymyr, Mudryk, Yaroslav, Hlova, Ihor, Dzevenko, Mariya, Havela, Ladislav, Kalychak, Yaroslav, Pecharsky, Vitalij, and Mudring, Anja-Verena. 2017. "EuNi 5 InH 1.5-x (x = 0–1.5): hydrogen induced structural and magnetic transitions". United States. doi:10.1039/c7tc00121e. https://www.osti.gov/servlets/purl/1347394.
@article{osti_1347394,
title = {EuNi 5 InH 1.5-x (x = 0–1.5): hydrogen induced structural and magnetic transitions},
author = {Bigun, Inna and Smetana, Volodymyr and Mudryk, Yaroslav and Hlova, Ihor and Dzevenko, Mariya and Havela, Ladislav and Kalychak, Yaroslav and Pecharsky, Vitalij and Mudring, Anja-Verena},
abstractNote = {The new quaternary hydride EuNi5InH1.5 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. EuNi5InH1.5 crystallizes in its own structure type (hP17, P6¯m2, 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. As a result, 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.},
doi = {10.1039/c7tc00121e},
journal = {Journal of Materials Chemistry. C},
number = 12,
volume = 5,
place = {United States},
year = {2017},
month = {1}
}

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