DOE OSTI2012
Neutron powder diffraction has been performed on the MTbF{sub 6} fluorides (M=Cd, Ca, Sr, ({alpha}/{beta})-Ba). Four of these fluorides (Cd, Ca, Sr, {beta}-Ba) are built of a (pseudo-) tetragonal packing of [TbF{sub 6}]{sup 2-} chains and only differs by the chains relative orientations. Thus this series represents a valuable opportunity to evaluate the Tb{sup 4+}-Tb{sup 4+} magnetic interactions. All the compounds displayed antiferromagnetic order (T{sub N}=2.70 K (Cd), 2.15 K (Ca), 2.60 K (Sr), 2.10 K ({beta}-Ba)), except for the {alpha} form of BaTbF{sub 6}. The crystal structure of this latter fluoroterbate has also been investigated by means of high-resolution neutron powder diffraction. From Neutron Powder Diffraction data, CdTbF{sub 6} and {beta}-BaTbF{sub 6} magnetic structures were determined, together with the metamagnetic behaviour of {beta}-BaTbF{sub 6} as a function of an external magnetic field. A tentative phase diagram is then given for {beta}-BaTbF{sub 6}. Advantage was taken of the polymorphism of the BaTbF{sub 6} fluoroterbate to analyse, on the basis of topological parameters such as bond distances and angles, the magnetic behaviour of its {alpha} and {beta} forms. It was shown that superexchange interactions are present in {beta}-BaTbF{sub 6}, and that these interactions may also rule the magnetic behaviour of the other MTbF{sub 6} (M=Ca, Sr, Cd) tetravalent terbium fluorides. - Graphical abstract: Powder neutron diffraction revealed magnetic order in four of the five investigated fluoroterbates, while crystal chemical analyses of {alpha} and {beta} forms of BaTbF{sub 6} evidenced the existence of superexchange interactions. Highlights: Black-Right-Pointing-Pointer Five fluoroterbates are investigated by Powder Neutron Diffraction (PND). Black-Right-Pointing-Pointer Four of them are antiferromagnetically ordered at 1.4 K. Black-Right-Pointing-Pointer Magnetic structures of {beta}-BaTbF{sub 6} and CdTbF{sub 6} are determined. Black-Right-Pointing-Pointer PND under magnetic field emphasises the metamagnetic behaviour of {beta}-BaTbF{sub 6}. Black-Right-Pointing-Pointer Comparison of {alpha} and {beta}-BaTbF{sub 6} evidences superexchange interactions in fluoroterbates.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗