Magnetic structures and excitations in sawtooth olivine chalcogenides Mn2SiX4 (X = S, Se).

The Mn lattice in olivine chalcogenide Mn2SiX4 (X = S, Se) compounds forms a sawtooth, which is of special interest in magnetism owing to the possibility of realizing flat bands in magnon spectra, a key component in magnonics. In this work, we investigate the Mn2SiX4 olivines using magnetic susceptibility, and X-ray and neutron diffraction. We have determined the average and local crystal structures of Mn2SiS4 and Mn2SiSe4 using synchrotron X-ray, neutron diffraction, and X-ray total scattering data followed by Rietveld and pair distribution function analyses. It is found from the pair distribution function analysis that the Mn triangle that constitutes the sawtooth is isosceles in Mn2SiS4 and Mn2SiSe4. The temperature evolution of magnetic susceptibility of Mn2SiS4 and Mn2SiSe4 shows anomalies below 83 K and 70 K, respectively, associated with magnetic ordering. From the neutron powder diffraction measurements the magnetic space groups of Mn2SiS4 and Mn2SiSe4 are found to be Pnma and Pnm'a', respectively. We find that the Mn spins adopt a ferromagnetic alignment on the sawtooth in both Mn2SiS4 and Mn2SiSe4 but along different crystallographic directions for the S and the Se compounds. From the temperature evolution of Mn magnetic moments obtained from refining neutron diffraction data, the transition temperatures are accurately determined as TN(S) = 83(2) K and TN(Se) = 70.0(5) K. Broad diffuse magnetic peaks are observed in both the compounds, and are prominently seen close to TN, suggesting the presence of a short-range magnetic order. The magnetic excitations studied using inelastic neutron scattering reveal a magnon excitation with an energy corresponding to approximately 4.5 meV in both S and Se compounds. Spin correlations are observed to persist up to 125 K much above the ordering temperature and we suggest the possibility of short-range spin correlations responsible for this.

Magnetocaloric Effect in a Frustrated Gd-Garnet with No Long-Range Magnetic Order.

In this paper, the hyperkagome lattice of Gd spins in a garnet compound, Gd3CrGa4O12, is studied using bulk measurements and density functional computations, and the observation of large magnetocaloric effect corresponding to an entropy change, ΔSm = 45 J kg-1K-1 (≈ 45 J mol-1K-1) at 2 K, 8 T is reported. Though the compound defies long-range magnetic order down to 0.4 K, a broad feature below 10 K is observed in the specific heat with two low temperature anomalies at T* ≈ 0.7 K and TS ≈ 2.45 K. The anomaly at T* is reminiscent of one in Gd3Ga5O12, where it is related to the development of a complex magnetic phase, whereas the TS-peak is accounted for by a multilevel Schottky-like model. The spin-lattice relaxation times studied by nuclear magnetic resonance experiments show that the relaxation is dominated by the magnetic fluctuations in Cr which has a longer relaxation time compared to that of the garnet, Lu3CrGa4O12 containing a nonmagnetic rare earth. Our first-principles density functional theory calculations agree well with the experimental results and support short-range magnetic order in the Gd-sublattice and antiferromagnetism in the Cr-sublattice. The importance of spin fluctuations and short-range order in the rare earth and transition metal lattices in garnets resulting in large magnetocaloric effect is brought out through this work.

Ammonothermal Synthesis, Crystal Structure, and Properties of the Ytterbium(II) and Ytterbium(III) Amides and the First Two Rare-Earth-Metal Guanidinates, YbC(NH)3 and Yb(CN3H4)3.

We report the oxidation-controlled synthesis of the ytterbium amides Yb(NH2)2 and Yb(NH2)3 and the first rare-earth-metal guanidinates YbC(NH)3 and Yb(CN3H4)3 from liquid ammonia. For Yb(NH2)2, we present experimental atomic displacement parameters from powder X-ray diffraction (PXRD) and density functional theory (DFT)-derived hydrogen positions for the first time. For Yb(NH2)3, the indexing proposal based on PXRD arrives at R3̅, a = 6.2477(2) Å, c = 17.132(1) Å, V = 579.15(4) Å(3), and Z = 6. The oxidation-controlled synthesis was also applied to make the first rare-earth guanidinates, namely, the doubly deprotonated YbC(NH)3 and the singly deprotonated Yb(CN3H4)3. YbC(NH)3 is isostructural with SrC(NH)3, as derived from PXRD (P63/m, a = 5.2596(2) Å, c = 6.6704(2) Å, V = 159.81(1) Å(3), and Z = 2). Yb(CN3H4)3 crystallizes in a structure derived from the [ReO3] type, as studied by powder neutron diffraction (Pn3̅, a = 13.5307(3) Å, V = 2477.22(8) Å(3), and Z = 8 at 10 K). Electrostatic and hydrogen-bonding interactions cooperate to stabilize the structure with wide and empty channels. The IR spectra of the guanidinates are compared with DFT-calculated phonon spectra to identify the vibrational modes. SQUID magnetometry shows that Yb(CN3H4)3 is a paramagnet with isolated Yb(3+) (4f(13)) ions. A CONDON 2.0 fit was used to extract all relevant parameters.