Structural Phase Transitions in SrRh2As2

SrRh2As2 exhibits structural phase transitions reminiscent to those of BaFe2As2, but crystallizes with three polymorphs derived from the tetragonal ThCr2Si2-type structure. The structure of alpha-SrRh2As2 is monoclinic with a = 421.2(1) pm, b = 1105.6(2) pm, c = 843.0(1) pm and beta = 95{deg} and was refined as a partially pseudo meroedric twin in the space group P21/c with R1 = 0.0928. beta-SrRh2As2 crystallizes with a modulated structure in the (3+1) dimensional superspace group Fmmm(10gamma)sigma 00 with the unit cell parameters a = 1114.4(3) pm, b = 574.4(2) pm and c = 611.5(2) pm and an incommensurable modulation vector q = (1, 0, 0.3311(4)). High temperature single crystal diffraction experiments confirm the tetragonal ThCr2Si2-type structure for gamma-SrRh2As2 above 350{deg}C. Electronic band structure calculations indicate that the structural distortion in alpha-SrRh2As2 is caused by strong Rh-Rh bonding interactions and has no magnetic origin as suggested for isotypic BaFe2As2.

Reducing the positional modulation of NbO6-octahedra in SrxBa1-xNb2O6 by increasing the Barium content: A single crystal neutron diffraction study at ambient temperature for x=0.61 and x=0.34

We report on the influence of the Barium content on the modulation amplitude in SrxBa1-xNb2O6 compounds by comparing Sr0.61Ba0.39Nb2O6 (SBN61) and Sr0.34Ba0.66Nb2O6 (SBN34). Our single crystal neutron diffraction results demonstrate that the amplitude of the positional modulation of the NbO6 octahedra is reduced with increasing barium content, indicating that the origin of the modulation is the partial occupation of the pentagonal channels by Sr and Ba atoms. By increasing the Sr content the bigger Ba atoms are replaced by the smaller Sr atoms, which leads to a larger deformation of the surrounding lattice and hence to a larger modulation amplitude. The more homogeneous the filling of these channels with one atomic type (Ba) the lower the modulation amplitude. Our results also show that the structure can be described with a two-dimensional incommensurate harmonic modulation. No second order modulation has been observed, both by single crystal diffraction measurements and q-scans. The positional modulation of the Nb atoms is much smaller than that of the oxygen atoms, such that the modulation can be seen as a rotational modulation of almost rigid NbO6-octahedra.