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

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

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

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

Upgrade of the diagnostic neutral beam injector for the TCV tokamak

A diagnostic neutral beam injector (DNBI) [CRPP report LRP 710/01, CRPP-EPFL, 200 1; EPS Conf. Comr. Fusion Plasma Phys., 25A (2001) 365] has been installed on tokamak A configuration variable (TCV) [Plasma Phys. Control Fusion, 36 (1994) 13277; Plasma Phys. Control Fusion, 43 (200 1) A 16 1; Plasma Phys. Control Fusion, to be published] for the purpose of providing local measurements of plasma ion temperature, velocity and impurity density by Charge exchange recombination spectroscopy (CXRS) [EPS Conf. Contr. Fusion Plasma Phys., 25A (2001) 365]. The system recently underwent a technical upgrade, which allowed to increase the full neutral beam current density by a factor of two (from 0.5 to 1 A at 52 keV injection energy) and to extend the operational range of the diagnostic. This was achieved by means of a new, larger ion source, with an increased extraction area and corresponding enhancements of the power supplies. (C) 2003 Elsevier B.V. All rights reserved

Synthesis and Characterization of MnCrO₄, a New Mixed-Valence Antiferromagnet

A new orthorhombic phase, MnCrO₄, isostructural with MCrO₄ (M = Mg, Co, Ni, Cu, Cd) was prepared by evaporation of an aqueous solution, (NH₄)₂Cr₂O₇ + 2 Mn­(NO₃)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⁺Cr⁶⁺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 <i>T</i>_N ≈ 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 <i>T</i>_N. MnCrO₄ is a semiconductor with activation energy of 0.27 eV; it loses oxygen on heating above 400 °C to form first Cr₂O₃ plus Mn₃O₄ and then Mn_1.5Cr_1.5O₄ spinel

Synthesis and Characterization of MnCrO₄, a New Mixed-Valence Antiferromagnet

A new orthorhombic phase, MnCrO₄, isostructural with MCrO₄ (M = Mg, Co, Ni, Cu, Cd) was prepared by evaporation of an aqueous solution, (NH₄)₂Cr₂O₇ + 2 Mn­(NO₃)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⁺Cr⁶⁺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 <i>T</i>_N ≈ 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 <i>T</i>_N. MnCrO₄ is a semiconductor with activation energy of 0.27 eV; it loses oxygen on heating above 400 °C to form first Cr₂O₃ plus Mn₃O₄ and then Mn_1.5Cr_1.5O₄ spinel

New Phase of MnSb₂O₆ Prepared by Ion Exchange: Structural, Magnetic, and Thermodynamic Properties

A new layered trigonal (<i>P</i>3̅1<i>m</i>) form of MnSb₂O₆, isostructural with MSb₂O₆ (M = Cd, Ca, Sr, Pb, and Ba) and MAs₂O₆ (M = Mn, Co, Ni, and Pd), was prepared by ion-exchange reaction between ilmenite-type NaSbO₃ and MnSO₄–KCl–KBr melt at 470 °C. It is characterized by Rietveld analysis of the X-ray diffraction pattern, electron microprobe analysis, magnetic susceptibility, specific heat, and ESR measurements as well as by density functional theory calculations. MnSb₂O₆ is very similar to MnAs₂O₆ in the temperature dependence of their magnetic susceptibility and spin exchange interactions. The magnetic susceptibility and specific heat data show that MnSb₂O₆ undergoes a long-range antiferromagnetic order with Néel temperature <i>T</i>_N = 8.5(5) K. In addition, a weak ferromagnetic component appears below <i>T</i>₁ = 41.5(5) K. DFT+U implies that the main spin exchange interactions are antiferromagnetic, thereby forming spin-frustrated triangles. The long-range ordered magnetic structure of MnSb₂O₆ is predicted to be incommensurate as found for MnAs₂O₆. On heating, the new phase transforms to the stable <i>P</i>321 form via its intermediate disordered variant