Possible quadrupolar nematic phase in the frustrated spin chain LiCuSbO4_4: an NMR investigation

The frustrated one-dimensional (1D) quantum magnet LiCuSbO$_4$ is one rare realization of the $J_1-J_2$ spin chain model with an easily accessible saturation field, formerly estimated to 12~T. Exotic multipolar nematic phases were theoretically predicted in such compounds just below the saturation field, but without unambiguous experimental observation so far. In this paper we present extensive experimental research of the compound in the wide temperature (30mK$-$300K) and field (0$-$13.3T) range by muon spin rotation ($\mu$SR), $^7$Li nuclear magnetic resonance (NMR) and magnetic susceptibility (SQUID). $\mu$SR experiments in zero magnetic field demonstrate the absence of long range 3D ordering down to 30mK. Together with former heat capacity data [S.E. Dutton \emph{et al}, Phys. Rev. Lett. 108, 187206 (2012)], magnetic susceptibility measurements suggest short range correlated vector chiral phase in the field range $0-4$T. In the intermediate field values (5$-$12T), the system enters in a 3D ordered spin density wave phase with 0.75$\mu_B$ per copper site at lowest temperatures (125mK), estimated by NMR. At still higher field, the magnetization is found to be saturated above 13T where the spin lattice $T_1^{-1}$ relaxation reveals a spin gap estimated to 3.2(2)K. We narrow down the possibility of observing a multipolar nematic phase to the range 12.5$-$13T.Comment: 12 pages, 15 figure

Effects of stoichiometric doping in superconducting Bi-O-S compounds.

Newly discovered Bi-O-S compounds remain an enigma in attempts to understand their electronic properties. A recent study of Bi4O4S3 has shown it to be a mixture of two phases, Bi2OS2 and Bi3O2S3, the latter being superconducting (Phelan et al 2013 J. Am. Chem. Soc. 135 5372-4). Using density functional theory, we explore the electronic structure of both the phases and the effect of the introduction of extra BiS2 bilayers. Our results demonstrate that the S2 layers dope the bismuth-sulphur bands and this causes metallisation. The bands at the Fermi level are of clear two-dimensional character. One band manifold is confined to the two adjacent, square-lattice bismuth-sulphur planes, a second manifold is confined to the square lattice of sulphur dimers. We show that the introduction of extra BiS2 bilayers does not influence the electronic structure. Finally, we also show that spin-orbit coupling does not have any significant effect on the states close to the Fermi level at the energy scale considered

Short-range ordering in a battery electrode, the 'cation-disordered' rocksalt Li1.25Nb0.25Mn0.5O2.

Cation order, with a local structure related to γ-LiFeO2, is observed in the nominally cation-disordered Li-excess rocksalt Li1.25Nb0.25Mn0.5O2via X-ray diffraction, neutron pair distribution function analysis, magnetic susceptibility and NMR spectroscopy. The correlation length of ordering depends on synthesis conditions and has implications for the electrochemistry of these phases.EPSRC: EP/L015978/1 Basic Energy Science, US Department of Energy: DE-SC001258

The Role of Ionic Liquid Breakdown in the Electrochemical Metallization of VO2: An NMR Study of Gating Mechanisms and VO2 Reduction.

Metallization of initially insulating VO2 via ionic liquid electrolytes, otherwise known as electrolyte gating, has recently been a topic of much interest for possible applications such as Mott transistors and memory devices. It is clear that the metallization takes place electrochemically, and, in particular, there has previously been extensive evidence for the removal of small amounts of oxygen during ionic liquid gating. Hydrogen intercalation has also been proposed, but the source of the hydrogen has remained unclear. In this work, solid-state magic angle spinning NMR spectroscopy (1H, 2H, 17O, and 51V) is used to investigate the thermal metal-insulator transition in VO2, before progressing to catalytically hydrogenated VO2 and electrochemically metallized VO2. In these experiments electrochemical metallization of bulk VO2 particles is shown to be associated with intercalation of hydrogen, the degree of which can be measured with quantitative 1H NMR spectroscopy. Possible sources of the hydrogen are explored, and by using a selectively deuterated ionic liquid, it is revealed that the hydrogenation is due to deprotonation of the ionic liquid; specifically, for the commonly used dialkylimidazolium-based ionic liquids, it is the "carbene" proton that is responsible. Increasing the temperature of the electrochemistry is shown to increase the degree of hydrogenation, forming first a less hydrogenated metallic orthorhombic phase then a more hydrogenated insulating Curie-Weiss paramagnetic orthorhombic phase, both of which were also observed for catalytically hydrogenated VO2. The NMR results are supported by magnetic susceptibility measurements, which corroborate the degree of Pauli and Curie-Weiss paramagnetism. Finally, NMR spectroscopy is used to identify the presence of hydrogen in an electrolyte gated thin film of VO2, suggesting that electrolyte breakdown, proton intercalation, and reactions with decomposition products within the electrolyte should not be ignored when interpreting the electronic and structural changes observed in electrochemical gating experiments.Oppenheimer Foundation The Winston Churchill Foundation of the United States Herchel Smith Scholarship EPSRC (EP/MO09521/1) EU H2020 program “Phase Change Switch” Alexander von Humboldt Foundatio

In situ observation of the magnetocaloric effect through neutron diffraction in the Tb(DCO2)3Tb(DCO_2)_3 and TbODCO3TbODCO_3 frameworks

Probing the magnetic structure of magnetocaloric materials in applied fields, can reveal detailed insight into the mechanism of magnetic refrigeration thereby linking the magnetic states that form under applied magnetic fields to changes in magnetic entropy. This study probes the long range magnetic order in $Tb(DCO_2)_3$ and $TbODCO_3$ as a function of temperature and applied magnetic field, through neutron diffraction measurements. A triangular Ising antiferromagnetic phase is formed, in small applied magnetic fields in $Tb(DCO_2)_3$, a spin flip transition occurs to a simple ferromagnetic structure in higher applied fields. $TbODCO_3$ undergoes a phase transition, in applied fields, into two magnetic phases; namely a buckled chain ferromagnetic phase along the b-axis and a canted antiferromagnetic phase, with a ferromagnetic component along c-axis. Both of the states observed in $TbODCO_3$ are consistent with Ising-like anisotropy previously reported in $TbODCO_3$ and the coexistance of these is likely the result of applying a magnetic field to a powdered sample

Raman study of magnetic excitations and magneto-elastic coupling in alpha-SrCr2O4

Using Raman spectroscopy, we investigate the lattice phonons, magnetic excitations, and magneto-elastic coupling in the distorted triangular-lattice Heisenberg antiferromagnet alpha-SrCr2O4, which develops helical magnetic order below 43 K. Temperature dependent phonon spectra are compared to predictions from density functional theory calculations which allows us to assign the observed modes and identify weak effects arising from coupled lattice and magnetic degrees of freedom. Raman scattering associated with two-magnon excitations is observed at 20 meV and 40 meV. These energies are in general agreement with our ab-initio calculations of exchange interactions and earlier theoretical predictions of the two-magnon Raman response of triangular-lattice antiferromagnets. The temperature dependence of the two-magnon excitations indicates that spin correlations persist well above the N\'eel temperature