Orbitally induced hierarchy of exchange interactions in zigzag antiferromagnetic state of honeycomb silver delafossite Ag3Co2SbO6

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

Preparation and characterization of metastable trigonal layered MSb2O6 phases (M = Co, Ni, Cu, Zn, and Mg) and considerations on FeSb2O6

MSb2O6 compounds (M = Mg, Co, Ni, Cu, Zn) are known in the tetragonal trirutile forms, slightly distorted monoclinically with M = Cu due to the Jahn-Teller effect. In this study, using a low-temperature exchange reaction between ilmenite-type NaSbO3 and molten MSO4-KCl (or MgCl2-KCl) mixtures, these five compositions were prepared for the first time as trigonal layered rosiaite (PbSb2O6)-type phases. Upon heating, they irreversibly transform to the known phases via amorphous intermediates, in contrast to previously studied isostructural MnSb2O6, where the stable phase is structurally related to the metastable phase. The same method was found to be applicable for preparing stable rosiaite-type CdSb2O6. The formula volumes of the new phases show an excellent correlation with the ionic radii (except for M = Cu, for which a Jahn-Teller distortion is suspected) and are 2-3% larger than those for the known forms although all coordination numbers are the same. The crystal structure of CoSb2O6 was refined via the Rietveld method: P31m, a = 5.1318(3) Å, and c = 4.5520(3) Å. Compounds with M = Co and Ni antiferromagnetically order at 11 and 15 K, respectively, whereas the copper compound does not show long-range magnetic order down to 1.5 K. A comparison between the magnetic behavior of the metastable and stable polymorphs was carried out. FeSb2O6 could not be prepared because of the 2Fe2+ + Sb5+ = 2Fe3+ + Sb3+ redox reaction. This electron transfer produces an additional 5s2 shell for Sb and results in a volume increase. A comparison of the formula volume for the stable mixture FeSbO4 + 0.5Sb2O4 with that extrapolated for FeSb2O6 predicted that the trirutile-type FeSb2O6 can be stabilized at high pressures. © 2017 The Royal Society of Chemistry.The work was supported by the Russian Foundation for Basic Research under the grant 14-03-01122. A. N. V. acknowledges the support in part from the Ministry of Education and Science of the Russian Federation in the framework of Increase Competitiveness Program of NUST (no. K2-2016-066) and by Act 211 of the Government of Russian Federation, contract no. 02.A03.21.0006

Static and dynamic magnetic response of fragmented haldane-like spin chains in layered Li3Cu2SbO6

The structure and the magnetic properties of layered Li3Cu2SbO6 are investigated by powder X-ray diffraction, static susceptibility, and electron spin resonance studies up to 330 GHz. The XRD data experimentally verify the space group C2=m with halved unit cell volume in contrast to previously reported C2=c. In addition, the data show significant Li=Cuintersite exchange. Static magnetic susceptibility and ESR measurements show two magnetic contributions, i.e., quasifree spins at low-temperature and a spin-gapped magnetic subsystem, with about half of the spins being associated to each subsystem. The data suggest ferromagnetic-antiferromagnetic alternating chains with JFM = -285 K and JAFM = 160 K with a significant amount of Li-defects in the chains. The results are discussed in the scenario of fragmented 1D S = 1 AFM chains with a rather high defect concentration of about 17% and associated S =1=2 edge states of the resulting finite Haldane chains. © 2016 The Physical Society of Japan

Synthesis and characterization of MnCrO4, a new mixed-valence antiferromagnet

A new orthorhombic phase, MnCrO4, isostructural with MCrO 4 (M = Mg, Co, Ni, Cu, Cd) was prepared by evaporation of an aqueous solution, (NH4)2Cr2O7 + 2 Mn(NO 3)2, followed by calcination at 400 C. It is characterized by redox titration, Rietveld analysis of the X-ray diffraction pattern, Cr K edge and Mn K edge XANES, ESR, magnetic susceptibility, specific heat and resistivity measurements. In contrast to the high-pressure MnCrO4 phase where both cations are octahedral, the new phase contains Cr in a tetrahedral environment suggesting the charge balance Mn2+Cr 6+O4. However, the positions of both X-ray absorption K edges, the bond lengths and the ESR data suggest the occurrence of some mixed-valence character in which the mean oxidation state of Mn is higher than 2 and that of Cr is lower than 6. Both the magnetic susceptibility and the specific heat data indicate an onset of a three-dimensional antiferromagnetic order at TN ≈ 42 K, which was confirmed also by calculating the spin exchange interactions on the basis of first principles density functional calculations. Dynamic magnetic studies (ESR) corroborate this scenario and indicate appreciable short-range correlations at temperatures far above T N. MnCrO4 is a semiconductor with activation energy of 0.27 eV; it loses oxygen on heating above 400 C to form first Cr 2O3 plus Mn3O4 and then Mn 1.5Cr1.5O4 spinel. © 2013 American Chemical Society

Study of the process e+e−→ηγ→7γe^+e^-\to\eta\gamma\to 7\gamma in the energy range s\sqrt{s} = 1.07 -- 2 GeV

The $e^+e^-\to\eta\gamma$ cross section is measured in the center-of-mass energy range from 1.07 to 2.00 GeV in the decay channel $\eta\to 3\pi^0$, $\pi^0\to\gamma\gamma$. The data set with an integrated luminosity of 242 pb$^{-1}$ accumulated in the experiment with the SND detector at the VEPP-2000 $e^+e^-$ collider is analyzed.Comment: 12 pages, 3 figures

[X-ray phase analysis of stag-horn concrements in citizens of south Russia].

It is known that recurrent nephroliths form in about half of the operated patients within 5 years after operation while 60% of all recurrences occur 3 years after removal of the primary concrement. To prevent recurrent nephroliths, it is important not only to detect metabolic disturbances but also to investigate chemical composition of uroliths. Mineral composition of 112 stag-horn concrements from patients living in the south of Russia was studied with x-ray phase analysis which showed that 62.9% concrements had mixed composition. Compared to patients with primary stag-horn nephrolithiasis, patients with recurrent one more often had calcium-phosphate and calcium-oxalate concrements than urate concrements. Chemical composition of the concrements depended on features of the relief of the region where the patients live. Newly established mineral characteristics of stag-horn concrements in the citizens of south Russia should be taken into consideration both in surgical treatment and follow-up of such patients