By combining experimental and computational studies, the orthorhombic stannide CeMgSn with a TiNiSi-type structure has been characterized as a potential hydrogen storage material. Experimental studies of the formed monohydride CeMgSnH including hydrogen absorption-desorption, thermal desorption spectroscopy, synchrotron and neutron powder diffraction (298 and 2 K), magnetization, and ¹¹⁹Sn Mössbauer spectroscopic measurements are discussed in parallel with ab initio electronic structure calculations. A small, 1.27 vol %, expansion of the unit cell of CeMgSn during its transformation into a thermally stable CeMgSnH monohydride is caused by an ordered insertion of H atoms into half of the available Ce₃Mg tetrahedral interstices leaving the CeMg₃ tetrahedra unoccupied. The bonding in CeMgSnH is dominated by strong Ce-Sn and Mg-Sn interactions which are almost not altered by hydrogenation, whereas the H atoms carry a small negative charge and show bonding interactions with Ce and Mg. Hydrogenation causes a conversion of the antiferromagnetic CeMgSn into ferromagnetic CeMgSnH with the Ce moments aligned along [001] with a magnetic moment of 1.4(3) μ_B. The ¹¹⁹Sn isomer shifts and the values of quadrupole splitting in the Mössbauer spectra suggest a similar s-electron density distribution for the Ce- and La-containing REMgSnH monohydrides.

The work was aimed on reaching a better understanding of the effect of magnesium as a component of the hydride-forming LaMgSn intermetallic compound crystallising with the orthorhombic TiNiSi type of structure on the hydrogenation behaviours, crystal structure and bonding interactions with hydrogen. The LaMgSn structure is significantly expanded as compared to the earlier studied isotypic LaNiSn H storage material (volume expansion of 23%), as a result of a substitution of the smaller Ni atoms by much larger Mg atoms. This significantly affects the chemistry of the interaction of the intermetallic compound with hydrogen because a transition metal, Ni, in replaced by an active hydride-forming metal, Mg. The work involved computational studies of the electronic structure of the intermetallic compound and its hydride, and experimental studies of the hydrogenation behaviour and thermal stability of the formed hydride LaMgSnH, its structural characterisation by SR XRD and neutron powder diffraction, and Mössbauer spectroscopic studies of the stannide and its hydride. These studies showed that in the system LaMgSn-H₂ a monohydride LaMgSnH is a thermodynamically favourable hydride composition. PDOS levels show that hydrogen and all constituting elemental metals, La, Mg and Sn, have peaks of electron density in the range between − 6 and − 4 eV indicating their hybridisation. The results show the hybridization of H atoms not only with bonded La and Mg atoms forming H-filled tetrahedra La₃Mg, but also with Sn despite its atoms do not have bonding interactions with H. This explains the high stability of the metal substructure which does not disproportionate into the binary hydrides of La and Mg even when heated to 200 °C @ 20 bar H₂, but instead forms an insertion type hydride. Formation of the monohydride LaMgSnH (Sp.gr. Pnma; a=8.1628(4); b= 4.5555(3); c= 9.2391(5) Å; V= 343.56(5) ų) causes a small (1.26%) expansion of the unit cell volume compared to LaMgSn, and mainly proceeds along the [100] direction. Hydrogen absorption-desorption cycle results in a reversible formation of the initial compound LaMgSn, with the peak of hydrogen release occurring in vacuum at 355 °C, which is intermediate between the temperatures for the vacuum decomposition of the dihydrides MgH₂ and LaH₂. From the combined refinements of the Synchrotron (SR) XRD and Neutron Powder Diffraction (NPD) data, deuterium atoms completely and in an ordered way fill a half of the available La₃Mg interstitial sites with metal-H/D distances of Mg-D= 2.026 Å; La-D= 2.381 and 2.502 Å. The occupied La₃Mg sites are smaller in size than the vacant Mg₃La tetrahedra. Sn and D exhibit a nonbonding interaction with the closest Sn-D separation of 3.033 Å. ¹¹⁹Sn Mössbauer spectra of LaMgSn and LaMgSnH show isomer shifts of 1.98(2) and 1.99(1) mm/s which are typical for the chemically similar stannides.