Search

The $A$MnO$_{2}$ delafossites ($A$=Na, Cu), are model frustrated antiferromagnets, with triangular layers of Mn$^{3+}$~spins. At low temperatures ($T_{N}$=65 K), a $C2/m \rightarrow P\overline{1}$ transition is found in CuMnO$_2$, which breaks frustration and establishes magnetic order. In contrast to this clean transition, $A$=Na only shows short-range distortions at $T_N$. Here we report a systematic crystallographic, spectroscopic, and theoretical investigation of CuMnO$_2$. We show that, even in stoichiometric samples, non-zero anisotropic Cu displacements co-exist with magnetic order. Using X-ray/neutron diffraction and Raman scattering, we show that high pressures acts to decouple these degrees of freedom. This manifests as an isostuctural phase transition at $\sim$10 GPa, with a reversible collapse of the $c$-axis. This is shown to be the high pressure analog of the $c$-axis negative thermal expansion seen at ambient pressure. DFT simulations confirm that dynamical instabilities of the Cu$^{+}$ cations and edge-shared MnO$_{6}$ layers are intertwined at ambient pressure. However, high pressure selectively activates the former, before an eventual predicted re-emergence of magnetism at the highest pressures. Our results show that the lattice dynamics and local structure of CuMnO$_2$ are quantitatively different to non-magnetic Cu delafossites, and raise questions about the role of intrinsic inhomogeniety in frustrated antiferromagnets., Comment: Submitted version, A.S.A.P. article in Inorganic Chemistry

The physical characterisation and understanding of molecular magnetic materials is one of the most important steps towards the integration of such systems in hybrid spintronic devices. Amongst the many characterisation techniques employed in such a task, Inelastic Neutron Scattering (INS) stands as one of the most powerful and sensitive tools to investigate their spin dynamics. Herein, the magnetic properties and spin dynamics of two dinuclear complexes, namely [(M(hfacac)$_2$)$_2$(bpym)] (where M = Ni$^{2+}$, Co$^{2+}$, abbreviated in the following as Ni$_2$, Co$_2$) are reported. These are model systems that could constitute fundamental units of future spintronic devices. By exploiting the highly sensitive IN5 Cold INS spectrometer, we are able to gain a deep insight into the spin dynamics of Ni$_2$ and to fully obtain the microscopic spin Hamiltonian parameters; while for Co$_2$, a multitude of INS transitions are observed demonstrating the complexity of the magnetic properties of octahedral cobalt-based systems.

The Ising triangular lattice remains the classic test-case for frustrated magnetism. Here we report neutron scattering measurements of short range magnetic order in CuMnO$_2$, which consists of a distorted lattice of Mn$^{3+}$ spins with single-ion anisotropy. Physical property measurements on CuMnO$_2$ are consistent with 1D correlations caused by anisotropic orbital occupation. However the diffuse magnetic neutron scattering seen in powder measurements has previously been fitted by 2D Warren-type correlations. Using neutron spectroscopy, we show that paramagnetic fluctuations persist up to $\sim$25 meV above TN= 65 K. This is comparable to the incident energy of typical diffractometers, and results in a smearing of the energy integrated signal, which hence cannot be analysed in the quasi-static approximation. We use low energy XYZ polarised neutron scattering to extract the purely magnetic (quasi)-static signal. This is fitted by reverse Monte Carlo analysis, which reveals that two directions in the triangular layers are perfectly frustrated in the classical spin-liquid phase at 75 K. Strong antiferromagnetic correlations are only found along the b-axis, and our results hence unify the pictures seen by neutron scattering and macroscopic physical property measurements.

We performed inelastic neutron scattering measurements on a polycrystalline sample of a classical kagome antiferromagnet NaBa$_{2}$Mn$_{3}$F$_{11}$ to investigate the possibility of a dispersionless zero-energy excitation associated with rotation of spins along the chains. The observed spectra indeed exhibit such an excitation with strong intensity at low energy, as well as dispersive excitations with weak intensity at high energy. Combining the measurements with calculations from linear spin-wave theory reveals that NaBa$_{2}$Mn$_{3}$F$_{11}$ is a good realization of the classical kagome antiferromagnet which exhibits a dispersionless mode lifted by the magnetic dipole-dipole interaction.

The hybrid halide perovskites MAPbI$_{3}$, MAPbI$_{2.94}$Cl$_{0.06}$, and MAPbCl$_{3}$ (MA - methylammonium) have been investigated using inelastic and quasielastic neutron scattering (QENS) with the aim of elucidating the impact of chloride substitution on the rotational dynamics of MA. In this context, we discuss the influence of the inelastic neutron scattering caused by low-energy phonons on the QENS resulting from the MA rotational dynamics in MAPbI$_{3-x}$Cl$_{x}$. Through a comparative temperature-dependent QENS investigation with different energy resolutions, which allow a wide Fourier time window, we achieved a consistent description of the influence of chlorine substitution in MAPbI$_{3}$ on to the MA dynamics. Our results show that chlorine substitution in the low temperature orthorhombic phase leads to a weakening of the hydrogen bridge bonds since the characteristic relaxation times of C$_{3}$ rotation at 70 K in MAPbCl$_{3}$ (135 ps) and MAPbI$_{2.94}$Cl$_{0.06}$ (485 ps) are much shorter than in MAPbI$_{3}$ (1635 ps). For the orthorhombic phase, we obtained the activation energies from the temperature-dependent characteristic relaxation times ${\tau}$C$_{3}$ by Arrhenius fits indicating lower values of E$_{a}$ for MAPbCl$_{3}$ and MAPbI$_{2.94}$Cl$_{0.06}$ compared to MAPbI$_{3}$. We also performed QENS analyses at 190 K for all three samples. Here we observed that MAPbCl$_{3}$ shows slower MA rotational dynamics than MAPbI$_{3}$ in the disordered structure., Comment: Corrected typos in Title and Abstract (

Spin fluctuations are widely believed to play an important role in the superconducting mechanisms of unconventional high-temperature superconductors. Spin fluctuations have been observed in iron-based superconductors as well. However, in some iron-based superconductors such as LaFePO$_{0.9}$, they have not been observed by inelastic neutron scattering (INS). LaFePO$_{0.9}$ is an iron-based superconductor with a low superconducting transition temperature ($T_{\rm c}$= 5 K), where line nodes are observed in the superconducting gap function. The line-node symmetry typically originates from sign reversal of the order parameter in spin-fluctuation-mediated superconductivity. This contradiction has been a long-standing mystery of this superconductor. Herein, spin fluctuations were found at high energies such as 30$-$50 meV with comparable intensities to an optimally doped LaFeAs(O,F). Based on this finding, the line-node symmetry can be explained naturally as spin-fluctuation-mediated superconductivity., Comment: 9 pages, 4 figures

Several Cu$^{2+}$ hydroxide minerals have recently been identified as candidate realizations of the $S=1/2$ kagome Heisenberg model. In this context, we have studied the distorted system KCu$_3$As$_2$O$_7$(OD)$_3$ using neutron scattering and bulk measurements. Although the distortion favors magnetic order over a spin liquid ground state, refinement of the magnetic diffraction pattern below $T_{N1}=7.05(5)$ K yields a complex helical structure with $\mathbf{k}=(0.77~0~0.11)$. This structure, as well as the spin excitation spectrum, are well described by a classical Heisenberg model with ferromagnetic nearest neighbor couplings. Multiferroicity is observed below $T_{N1}$, with an unusual crossover between improper and pseudo-proper behavior occurring at $T_{N2}=5.5$ K. The polarization at $T=2$ K is $P=1.5 \mu$Cm$^{-2}$. The properties of KCu$_3$As$_2$O$_7$(OD)$_3$ highlight the variety of physics which arise from the interplay of spin and orbital degrees of freedom in Cu$^{2+}$ kagome systems., Comment: Accepted for publication in Phys. Rev. B

Rattling dynamics have been identified as fundamental to superconductivity in defect pyrochlore osmates and aluminium vanadium intermetallics, as well as low thermal conductivity in clathrates and filled skutterudites. Combining inelastic neutron scattering (INS) measurements and ab initio molecular dynamics (MD) simulations, we use a new approach to investigate rattling in the Al-doped defect pyrochlore tungstates: AAl0.33W1.67O6 (A = K, Rb, Cs). We find that although all the alkali metals rattle, the rattling of the K atoms is unique, involving local diffusion within a cage as well as vibrations at a range of frequencies. We show that the novel K rattling is driven by the strong anharmonicity and anisotropy of the local potentials around the K atoms, both of which are a consequence of the small size of the K rattler. Our findings may open new possibilities for phonon engineering in thermoelectric materials., Comment: 17 pages, 12 figures and 3 tables

The dynamical magnetic correlations in \tbti\, have been investigated using polarized inelastic neutron scattering. Dispersive excitations are observed, emerging from pinch points in reciprocal space and characterized by an anisotropic spectral weight. Anomalies in the crystal field and phonon excitation spectrum at Brillouin zone centers are also reported. These findings suggest that Coulomb phases, although they present a disordered ground state with dipolar correlations, allow the propagation of collective excitations. They also point out a strong spin-lattice coupling, which likely drives effective interactions between the $4f$ quadrupolar moments.

Geometrical frustration is a central challenge in contemporary condensed matter physics, a crucible favourable to the emergence of novel physics. The pyrochlore magnets, with rare earth magnetic moments localized at the vertices of corner-sharing tetrahedra, play a prominent role in this field, with a rich variety of exotic ground states ranging from the "spin ices" \hoti\ and \dyti\ to the "spin liquid" and "ordered spin ice" ground states in \tbti\ and \tbsn. Inelastic neutron scattering provides valuable information for understanding the nature of these ground states, shedding light on the crystal electric field (CEF) level scheme and on the interactions between magnetic moments. We have performed such measurements with unprecedented neutron flux and energy resolution, in the "ordered spin ice" \tbsn. We argue that a new interaction, which involves the spin lattice coupling through a low temperature distortion of the trigonal crystal field, is necessary to account for the data.

We report a combination of physical property and neutron scattering measurements for polycrystalline samples of the one-dimensional spin chain compound CoV2O6. Heat capacity measurements show that an effective S = 1/2 state is found at low temperatures and that magnetic fluctuations persist up to 6.Tn. Above Tn = 6.3 K, measurements of the magnetic susceptibility as a function of T and H show that the nearest neighbour exchange is ferromagnetic. In the ordered state, we have discovered a crossover from a metamagnet with strong fluctuations between 5 K and Tn to a state with a 1/3 magnetisation plateau at 2 < T < 5 K. We use neutron powder diffraction measurements to show that the AFM state has incommensurate long range order and inelastic time of flight neutron scattering to examine the magnetic fluctuations as a function of temperature. Above Tn, we find two broad bands between 3.5 and 5 meV and thermally activated low energy features which correspond to transitions within these bands. These features show that the excitations are deconfined solitons rather than the static spin reversals predicted for a uniform FM Ising spin chain. Below Tn, we find a ladder of states due to the confining effect of the internal field. A region of weak confinement below Tn, but above 5 K, is identified which may correspond to a crossover between 2D and 3D magnetic ordering., Comment: Expanded version, includes results from arXiv:0804.2966 and neutron powder diffraction. To appear in PRB

CuCrS2 is a triangular lattice Heisenberg antiferromagnet with a rhombohedral crystal structure. We report on neutron and synchrotron powder diffraction results which reveal a monoclinic lattice distortion at the magnetic transition and verify a magnetoelastic coupling. CuCrS2 is therefore an interesting material to study the influence of magnetism on the relief of geometrical frustration., Comment: 6 pages, 6 figures, 1 table

We report a detailed study of specific heat, electrical resistivity and thermal expansion in combination with inelastic neutron and inelastic X-ray scattering to investigate the origin of superconductivity in the two silicon clathrate superconductors Ba8Si46 and Ba24Si100. Both compounds have a similar structure based on encaged barium atoms in oversized silicon cages. However, the transition temperatures are rather different: 8 K and 1.5 K respectively. By extracting the superconducting properties, phonon density of states, electron-phonon coupling function and phonon anharmonicity from these measurements we discuss the important factors governing Tc and explain the difference between the two compounds., Comment: 31 pages, 2 tables, 12 figures

The anisotropy splitting in the ground state of the single-molecule magnet [Mn4O3Br(OAc)3(dbm)3] is studied by inelastic neutron scattering as a function of hydrostatic pressure. This allows a tuning of the anisotropy and thus the energy barrier for slow magnetisation relaxation at low temperatures. The value of the negative axial anisotropy parameter $D_{\rm cluster}$ changes from -0.0627(1) meV at ambient to -0.0603(3) meV at 12 kbar pressure, and in the same pressure range the height of the energy barrier between up and down spins is reduced from 1.260(5) meV to 1.213(9) meV. Since the $\rm Mn-Br$ bond is significantly softer and thus more compressible than the $\rm Mn-O$ bonds, pressure induces a tilt of the single ion Mn$^{3+}$ anisotropy axes, resulting in the net reduction of the axial cluster anisotropy., Comment: 4 pages, 3 figures

A high resolution inelastic neutron scattering (INS) study of fully deuterated Mn$_{12}$-acetate provides the most accurate spin Hamiltonian parameters for this prototype single molecule magnet so far. The Mn$_{12}$-clusters deviate from axial symmetry, a non-zero rhombic term in the model Hamiltonian leading to excellent agreement with observed positions and intensities of the INS peaks. The following parameter set provides the best agreement with the experimental data: $D=-0.0570(1)$ meV, $B_{4}^0=-2.78(7)\cdot 10^{-6}$ meV, $B_{4}^4=-3.2(6)\cdot 10^{-6}$ meV and $\mid$\textit{E}$\mid =6.8(15)\cdot 10^{-4}$ meV. Crystal dislocations are not the likely cause of the symmetry lowering. Rather, this study lends strong support to a recently proposed model, which is based on the presence of several molecular isomers with distinct spin Hamiltonian parameters., Comment: 4 pages, 4 figures