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The crystal structures of monoclinic samarium and cubic europium sesquioxide, Sm 2 O 3  and Eu 2 O 3 , were reinvestigated by powder diffraction methods (laboratory X-ray, synchrotron, neutron). Rietveld analysis yields more precise structural parameters than previously known, especially for oxygen atoms. Interatomic distances  d (Sm–O) in Sm 2 O 3  range from 226.3(4) to 275.9(2) pm [average 241.6(3) pm] for the monoclinic  B  type Sm 2 O 3  [space group  C 2/ m ,  a  = 1418.04(3) pm,  b  = 362.660(7) pm,  c  = 885.48(2) pm,  β  = 100.028(1)°],  d (Eu–O) in Eu 2 O 3  from 229.9(2) to 238.8(2) pm for the cubic bixbyite ( C ) type [space group  Ia 3̅,  a  = 1086.87(1) pm]. Neutron diffraction at 50 K and 2 K did not show any sign for magnetic ordering in Sm 2 O 3 . Isotopically enriched  154 Sm 2 O 3  and  153 Eu 2 O 3  were used for the neutron diffraction work because of the enormous absorption cross section of the natural isotopic mixtures for thermal neutrons. The isotopic purity was determined by inductively coupled plasma – mass spectrometry to be 98.9% for  154 Sm and 99.8% for  153 Eu. Advanced analysis of the neutron diffraction data suggest that the bound coherent scattering lengths of  154 Sm and  153 Eu need to be revised. We tentatively propose  b  c ( 154 Sm) = 8.97(6) fm and  b  c ( 153 Eu) = 8.85(3) fm for a neutron wavelength of 186.6 pm to be better values for these isotopes, showing up to 8% deviation from accepted literature values. It is shown that inaccurate scattering lengths may result in severe problems in crystal structure refinements causing erroneous structural details such as occupation parameters, which might be critically linked to physical properties like superconductivity in multinary oxides.

zeitschrift für kristallographie - crystalline materials

Crystal structure of monoclinic samarium and cubic europium sesquioxides and bound coherent neutron scattering lengths of the isotopes  154 Sm and  153 Eu