Search

Recent theoretical studies have suggested that Kitaev physics and such effects as formation of a mysterious spin-liquid state can be expected not only in RuCl3 and iridates, but also in conventional $3d$ transition metal compounds. Using DC and AC magnetometry, thermodynamic and $^{23}$Na nuclear magnetic resonance measurements (NMR) we studied such a candidate material Na3Co2SbO6. A full phase diagram of Na3Co2SbO6 in a wide range of magnetic fields and temperatures is presented. The results demonstrate transformation of the antiferromagnetic structure under the external magnetic field, gradual development of the saturation phase, as well as evidence of gapped behavior in certain parts of the phase diagram

Li3Co2SbO6 is prepared by molten salt ion exchange and its structure refined by the Rietveld method confirming the honeycomb-type Co/Sb ordering of its Na precursor. Monoclinic rather than trigonal symmetry of Na3Co2SbO6 is directly demonstrated for the first time by peak splitting in the high-resolution synchrotron XRD pattern. The long-range antiferromagnetic order is established at TN about 6.7 K and 9.9 K in Na3Co2SbO6 and Li3Co2SbO6, respectively, confirmed by both the magnetic susceptibility and specific heat. Spin-wave analysis of specific heat data indicates the presence of 3D AFM magnons in Na3Co2SbO6 and 2D AFM magnons in Li3Co2SbO6. The field dependence of the magnetization almost reaches saturation in moderate magnetic fields up to 9 T and demonstrates characteristic features of magnetic field induced spin-reorientation transitions for both A3Co2SbO6 (A = Na, Li). Overall thermodynamic studies show that the magnetic properties of both compounds are very sensitive to an external magnetic field, thus predicting a non-trivial ground state with a rich magnetic phase diagram. The ground state spin configuration of Li3Co2SbO6 has been determined by low-temperature neutron powder diffraction. It represents a ferromagnetic arrangement of moments in the honeycomb layers with antiferromagnetic coupling between adjacent layers.

The manganese tellurate Li2MnTeO6 consists of trigonal spin lattices made up of Mn4+ (d3, S = 3/2) ions. The magnetic properties of this compound were characterized by several experimental techniques, which include magnetic susceptibility, specific heat, dielectric permittivity, electron spin resonance (ESR), nuclear magnetic resonance (NMR) and neutron powder diffraction (NPD) measurements, and by density functional calculations (DFT). The magnetic susceptibility chi(T) demonstrates very unusual behavior. It isdescribed by the Curie-Weiss law at high temperature with Curie-Weiss temperature of Theta = -74 K, exhibits no obvious anomaly indicative of a long-range magnetic ordering at low magnetic fields. At high magnetic fields, however, the character of chi(T) changes showing a maximum at about 9 K. That this maximum of chi(T) reflects the onset of an antiferromagnetic order was confirmed by specific heat measurements, which exhibit a clear lambda-type anomaly at TN around 8.5 K even at zero magnetic field, and by 7Li NMR and dielectric permittivity measurements. The magnetic structure of Li2MnTeO6, determined by neutron powder diffraction measurements at 1.6 K, is described by the 120-degree non-collinear spin structure with the propagation vector k = (1/3, 1/3, 0). Consistent with this finding, the spin exchange interactions evaluated for Li2MnTeO6 by density functional calculations are dominated by the nearest-neighbor antiferromagnetic exchange within each triangular spin lattice. This spin lattice is strongly spin frustrated with f = |Theta|/TN around 8 and exhibits a two-dimensional magnetic character in a broad temperature range above TN.

Ion-exchange treatment of Na2SnTeO6 in molten salt mixtures resulted in rosiaite (PbSb2O6)-related MnSnTeO6. Its crystal structure was refined by the Rietveld method. Of the three possible models of Sn/Te distribution, the disordered model ((P3 Im, a = 5.23093(11) A, c = 4.62430(16) A was preferred based on bond distances. However, it is supposed that each individual (SnTeO6)2- layer retains complete ordering of the precursor and the apparent disorder is only due to stacking faults. The magnetic studies have shown that MnSnTeO6 orders antiferromagnetically at Neel temperature TN = 9.8 K. The effective magnetic moment reasonably agrees with theoretical estimations assuming high-spin configuration of Mn2+ (S = 5/2). Electron spin resonance reveals spin dynamics in accordance with aniferromagnetic ordering with critical broadening of ESR linewidth indicating the low-dimentional type of exchange interactions. Based on the temperature and field-dependent magnetization studies, the magnetic phase diagram of the new compound was constructed.

MnSnTeO6, a new chiral antiferromagnet, was prepared both by topotactic transformation of the metastable rosiaite-type polymorph and by direct synthesis from coprecipitated hydroxides. Its structure, static and dynamic magnetic properties were studied comprehensively both experimentally (through X-ray and neutron powder diffraction, magnetization, specific heat, dielectric permittivity and ESR techniques) and theoretically (by means of ab initio density functional theory (DFT) calculations within the spin-polarized generalized gradient approximation). MnSnTeO6 is isostructural with MnSb2O6 (space group P321) and does not show any structural transition between 3 and 300 K. The magnetic susceptibility and specific heat exhibit an antiferromagnetic ordering at TN=9.8 K, which is confirmed by low-temperature neutron data. At the same time, the thermodynamic parameters demonstrate an additional anomaly on the temperature dependences of magnetic susceptibility chi(T), specific heat Cp(T) and dielectric permittivity epsilon(T) at T*=4.9 K, which is characterized by significant temperature hysteresis. Clear enhancement of the dielectric permittivity at T* is most likely to reflect the coupling of dielectric and magnetic subsystems leading to development of electric polarization. It was established that the ground state of MnSnTeO6 is stabilized by seven exchange parameters, and neutron diffraction revealed incommensurate magnetic structure with propagation vector k= (0, 0, 0.183) analogous to that of MnSb2O6. Ab initio DFT calculations demonstrate that the strongest exchange coupling occurs between planes along diagonals. All exchange parameters are antiferromagnetic and reveal moderate frustration.

The decisive role of magnetic anisotropy even in systems with small anisotropy is illustrated for the honeycomb-layered antiferromagnets The decisive role of magnetic anisotropy in honeycomb layered Li$_3$Ni$_2$SbO$_6$ and Na$_3$Ni$_2$SbO$_6$ with $A$ = Li and Na. Both systems evolve long range magnetic order below $T_{\rm N}$ = 14 and 16.5~K, respectively. The magnetic phase diagrams obtained from static magnetisation studies up to 15~T imply competing antiferromagnetic phases and a tricritical point at $T_{\rm N}$. The phase boundaries are visible in the dynamic response of the antiferromagnetic resonance modes, too, which investigation by means of high frequency/high field electron spin resonance enables precise determination of magnetic anisotropy. The anisotropy gap amounts to $\Delta = 360 \pm 2$~GHz in Na$_3$Ni$_2$SbO$_6$ while in Li$_3$Ni$_2$SbO$_6$ orthorhombicity is associated with $\Delta = 198 \pm 4$ and $218 \pm 4$~GHz. Above $T_{\rm N}$, the data imply short-range antiferromagnetic order up to at least 80~K. The data suggest a crucial role of anisotropy for selecting the actual spin structure at $B=0$~T.

Static and dynamic magnetic properties of P\={3}1$m$-phase MnSb$_2$O$_6$ have been studied by means of muon spin relaxation ($\mu$SR), high-frequency electron spin resonance (HF-ESR), specific heat, and magnetisation studies in magnetic fields up to 25\,T. The data imply onset of long-range antiferromagnetic order at $T_N$ =~8~K and a spin-flop-like transition at $B_{SF}\approx 0.7 - 1$~T. Below $T_N$, muon asymmetry exhibits well-defined oscillations indicating a narrow distribution of the local fields. A competing antiferromagnetic phase appearing below $T_2$ =~5.3~K is evidenced by a step in the magnetisation and a slight kink of the relaxation rate. Above $T_N$ , both $\mu$SR and HF-ESR data suggest short-range spin order. HF-ESR data show that local magnetic fields persist up to at least $12\cdot T_{\rm N}\approx 100$\,K. Analysis of the antiferromagnetic resonance modes and the thermodynamic spin-flop field suggest zero-field splitting of $\Delta \approx 18$\,GHz which implies small but finite magnetic anisotropy.

The magnetic phase diagram and low-energy magnon excitations of structurally and magnetically chiral MnSb2O6 are reported. The specific heat and the static magnetization are investigated in magnetic fields up to 9 and 30 T, respectively, while the dynamicmagnetic properties are probed by X-band as well as tunable high-frequency electron spin-resonance spectroscopy. Below TN = 11.5 K, we observe antiferromagnetic resonance modes which imply small but finite planar anisotropy showing up in a zero-field splitting of 20 GHz. The data are well described by means of an easy-plane two-sublattice model with the anisotropy field BA = 0.02 T. The exchange field BE = 13 T is obtained from the saturation field derived from the pulsed-field magnetization. A crucial role of the small anisotropy for the spin structure is reflected by competing antiferromagnetic phases appearing, at T = 2 K, in small magnetic fields at BC1 $\approx$ 0.5 T and BC2 = 0.9 T. We discuss the results in terms of spin reorientation and of small magnetic fields favoring helical spin structure over the cycloidal ground state which, at B = 0, is stabilized by the planar anisotropy. Above TN, short-range magnetic correlations up to >=60 K and magnetic entropy changes well above TN reflect the frustrated triangular arrangement of Mn2+ ions in MnSb2O6.

We report the revised crystal structure, static and dynamic magnetic properties of quasi-two dimensional honeycomb-lattice silver delafossite Ag3Co2SbO6. The magnetic susceptibility and specific heat data are consistent with the onset of antiferromagnetic long range order at low temperatures with N\'eel temperature TN ~ 21.2 K. In addition, the magnetization curves revealed a field-induced (spin-flop type) transition below TN in moderate magnetic fields. The GGA+U calculations show the importance of the orbital degrees of freedom, which maintain a hierarchy of exchange interaction in the system. The strongest antiferromagnetic exchange coupling was found in the shortest Co-Co pairs and is due to direct and superexchange interactions between the half-filled xz+yz orbitals pointing directly to each other. The other four out of six nearest neighbor exchanges within the cobalt hexagon are suppressed, since for these bonds active half-filled orbitals turned out to be parallel and do not overlap. The electron spin resonance (ESR) spectra reveal a Gaussian shape line attributed to Co2+ ion in octahedral coordination with average effective g-factor g=2.3+/-0.1 at room temperature and shows strong divergence of ESR parameters below 120 K, which imply an extended region of short-range correlations. Based on the results of magnetic and thermodynamic studies in applied fields, we propose the magnetic phase diagram for the new honeycomb-lattice delafossite.