International Union of Crystallography, Acta Crystallographica Section B: Structural Science, Crystal Engineering and Materials, 6(79), p. 473-481, 2023
DOI: 10.1107/s205252062300817x
Full text: Unavailable
The magnetic structure of chromium arsenide CrAs is studied with neutron powder diffraction at ambient pressure in the temperature range 1.5–300 K as well as with neutron single-crystal diffraction at 2 K and 0.12 GPa. The material undergoes an anti-isostructural phase transition at T N = 267 K and atmospheric conditions, in which both orthorhombic phases have the same space-group symmetry (Pnma, Z = 4) but different distortions of the parent hexagonal structure of the NiAs type (P63/mmc, Z = 2). The magnetic structure below T N is incommensurate with the propagation vector k = (0, 0, k c). At ambient pressure, the component k c decreases from k c = 0.3807 (7) at 260 K to k c = 0.3531 (6) at 50 K. Below this temperature, it is basically constant. With increasing pressure at 2 K, k c is also constant within standard uncertainties [k c = 0.353 (2)]. For the analysis of the magnetic structure, a group-theoretical approach based on the space group of the nuclear structure and its subgroups is used. To avoid falling into false minima in the refinements, a random search for magnetic moments in the models is implemented. In the literature, the magnetic structure has been determined on the basis of powder diffraction data as a double helix propagating along the c axis. Although this double-helical model leads to satisfactory agreement factors for our powder data, it does not reproduce the intensities of the magnetic satellite reflections measured on single-crystal data in a satisfactory way and can therefore be discarded. Instead, several other models are found that lead to better agreement. Each of them is spiral-like with directional components in all three directions and with no spin-density wave character that would cause a non-constant magnetic moment. In all these models, the ordering of the spins is neither a pure helix nor a pure cycloid. Instead, the unit vectors of the spin rotation planes make an angle α, 0° < α < 90°, with respect to the c* direction. The model in superspace group P21.1′(α0γ)0s yields the best agreement factors in the refinements of the neutron single-crystal and powder diffraction data. This model is unique as it is the only one in which all the magnetic moments rotate with the same chirality.