| Article ID | Journal | Published Year | Pages | File Type |
|---|---|---|---|---|
| 1504691 | Solid State Sciences | 2013 | 8 Pages |
•Synthesis of the germanides UMnGe and U2Mn3Ge.•Structure refinement from X-ray powder data.•DFT calculations.
The title compounds were prepared by induction levitation melting of the elemental components and subsequent annealing. UMnGe (Pnma, a = 686.12(9), b = 425.49(6) and c = 736.5(1) pm) adopts the orthorhombic structure of TiNiSi and U2Mn3Ge (P63/mmc, a = 524.3(2) and c = 799.2(3) pm) possesses the hexagonal Mg2Cu3Si-type structure (ordered variant of the hexagonal Laves phase MgZn2). Both structures were refined from X-ray powder data to residuals of RI = 0.021 and 0.014 for UMnGe and U2Mn3Ge, respectively. The manganese and germanium atoms in UMnGe build up a three-dimensional [MnGe] network of ordered Mn3Ge3 hexagons with Mn–Ge distances ranging from 248 to 259 pm. The uranium atoms are coordinated by two tilted Mn3Ge3 hexagons. The manganese atoms in U2Mn3Ge build up Kagomé networks with 252 and 272 pm Mn–Mn distances which are connected via the germanium atoms (254 pm Mn–Ge) to a three-dimensional network. A remarkable feature of the U2Mn3Ge structure is a short U–U distance of 278 pm between adjacent cavities of the [Mn3Ge] network. From DFT based electronic structure calculations both germanides are found more cohesive than the Laves phase UMn2, thus underpinning the substantial role of Mn–Ge bonding. Calculations for both germanides show ferrimagnetic ground states with antiparallel spin alignments between U and Mn. The valence bands show bonding characteristics for interactions of atoms of different chemical natures and significant Mn–Mn bonding in U2Mn3Ge. Preliminary investigation of UMnGe by magnetization measurements confirms an antiferromagnetic arrangement below TN = 240 K.
Graphical abstractFigure optionsDownload full-size imageDownload as PowerPoint slide
