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Among the large class of $A$-site ordered perovskites of stoichiometry $A{C}_{3}{B}_{4}{\mathrm{O}}_{12}$, the rare-earth $(R)$ ruthenates $R{\mathrm{Cu}}_{3}{\mathrm{Ru}}_{4}{\mathrm{O}}_{12}$ $(R=\mathrm{La}, \mathrm{Pr}, \mathrm{Nd})$ are interesting compounds due both to $\mathrm{Ru}\text{\ensuremath{-}}4d$-derived electronic correlations and to unconventional crystal-electric-field effects of the $R$ ions. Here we report on detailed investigations of these compounds utilizing x-ray diffraction, neutron scattering, magnetic susceptibility, and electrical resistivity measurements as well as heat capacity and nuclear resonance experiments. A broad range of external parameters is scanned and depending on the specific technique, temperatures range from 100 mK to 730 K in external magnetic fields up to 14 T. In this work ${\mathrm{LaCu}}_{3}{\mathrm{Ru}}_{4}{\mathrm{O}}_{12}$ serves as reference compound with a nonmagnetic $A$ site, characterized in detail recently [S. Riegg et al., Phys. Rev. B 93, 115149 (2016)]. All compounds investigated reveal heavy-fermion behavior with a ${T}^{2}$ dependence of the low-temperature electrical resistivity and significantly enhanced Sommerfeld coefficients. Toward low temperatures, the compounds with $R=\mathrm{Pr}$ and Nd are dominated by the magnetic moments of the $R$ ions, which occupy crystallographic positions with point-group symmetry ${T}_{h}$. The crystal-electric-field effects are clearly visible especially in heat capacity and inelastic neutron scattering data from which the crystal-electric-field parameters are derived. The ground state of the ${\mathrm{Pr}}^{3+}$ ion is identified as a triplet $({\mathrm{\ensuremath{\Gamma}}}_{4}^{(1)})$, whereas for ${\mathrm{Nd}}^{3+}$ it is a quartet $({\mathrm{\ensuremath{\Gamma}}}_{67})$. Evidence for lowering of the ${T}_{h}$ symmetry is observed at the Pr site at temperatures below 10 K, suggesting the formation of orbital order. Moreover, the spin-lattice relaxation derived from $^{63}\mathrm{Cu}$ nuclear quadrupole resonance indicates characteristic temperatures close to 7 K and 350 mK, probably related to orbital and magnetic order, respectively.

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

The low lattice thermal conductivity in inorganic clathrates has been shown recently to be related to the low-energy range of optical phonons dominated by motions of guest atoms trapped in a network of host covalent cages. A promising route to further reduce the heat conduction, and increase the material efficiency for thermoelectric heat waste conversion, is then to lower the energy of these guest-weighted optical phonons. In the present work, the effect of the host cage geometry is explored. The lattice dynamics of the binary type-IX clathrate, Ba24Si100, has been investigated experimentally by means of inelastic neutron scattering as a function of temperature between 5 K and 280 K, and computed by ab-initio density functional techniques. It is compared with the lattice dynamics of Ba8Si46, the simplest representative of the well-known type-I clathrate structure. The binary Ba8Si46 and Ba24Si100 materials have both a cubic unit cell made of different Si cages. The energies, the degree of anharmonicity as well as the anisotropy of the optical phonon modes weighted by Ba motions are found to depend strongly on 2 the size and shape of the cages. The lowest optical phonon energies in Ba24Si100 are found around 2.5-4 meV, while those in Ba8Si46 have higher energies around 7-9 meV. The low-lying optical phonons in Ba24Si100 are mainly weighted by the motion of Ba in the opened Si20 cage, which doesn't exist in Ba8Si46. Moreover, the Ba vibrations within the opened Si20 cages are found intrinsically anisotropic, strongly dispersionless in some directions and exhibit a significant anharmonicity, which is not observed for any optical phonon modes in Ba8Si46.

We performed inelastic neutron scattering measurements on a polycrystalline sample of a classical kagome antiferromagnet ${\mathrm{NaBa}}_{2}{\mathrm{Mn}}_{3}{\mathrm{F}}_{11}$ 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 ${\mathrm{NaBa}}_{2}{\mathrm{Mn}}_{3}{\mathrm{F}}_{11}$ is a good realization of the classical kagome antiferromagnet which exhibits a dispersionless mode lifted by the magnetic dipole-dipole interaction.

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.

CeCuAl3 crystallizing in the tetragonal BaNiSn3-type structure and CeCuxAl4–x solid solutions were investigated by means of elastic and inelastic neutron scattering. Powder neutron diffraction brought information on both temperature evolution of crystallographic parameters and magnetic order at low temperatures. No structural change was observed in the investigated temperature range from 1.5 to 300 K. Weak magnetic peaks outside nuclear Bragg positions observed in solid solutions with 0.90 ≤ x ≤ 1.10 were described by the propagation vector k = (0.40 + δx, 0.60 + δy, 0), where δx ≈ 0.02 and δy ≈ 0.01. The magnetic structure of CeCu0.75Al3.25 consists of two components: an anti-ferromagnetic one described by the same k and a ferromagnetic one with k0 = (0, 0, 0) and magnetic moments lying within the tetragonal basal plane. The evolution of magnetic excitations as a function of Cu–Al concentration in CeCuxAl4–x was studied by inelastic neutron scattering. The measured spectra of CeCuAl3 and the solution wit...

The instrumental divergence parameters and resolution for the D7 neutron diffuse scattering spectrometer at the Institut Laue-Langevin, France, are presented. The resolution parameters are calibrated against measurements of powders, single crystals, and the incoherent scattering from vanadium. We find that the powder diffraction resolution is well described by the Cagliotti function, the single crystal resolution function can be parameterized using the Cooper-Nathans formalism, and that in time-of-flight mode the energy resolution is consistent with monochromatic focussing.

Tb2Ti2O7 presents an ongoing conundrum in the study of rare-earth pyrochlores. Despite the expectation that it should be the prototypical unfrustrated noncollinear Ising antiferromagnet on the pyrochlore lattice, it presents a puzzling correlated state that persists to the lowest temperatures. Effects which can reintroduce frustration or fluctuations are therefore sought, and quadrupolar operators have been implicated. One consequence of strong quadrupolar effects is the possible coupling of magnetic and lattice degrees of freedom, and it has previously been shown that a hybrid magnetoelastic mode with both magnetic and phononic character is formed in Tb2Ti2O7 by the interaction of a crystal field excitation with a transverse-acoustic phonon. Here, using polarized and unpolarized inelastic neutron scattering, we present a detailed characterization of the magnetic and phononic branches of this magnetoelastic mode, particularly with respect to their composition, the anisotropy of any magnetic fluctuations, and also the temperature dependence of the different types of fluctuation that are involved. We also examine the dispersion relations of the exciton branches that develop from the crystal field excitation in the same temperature regime that the coupled mode appears, and find three quasidispersionless branches where four are expected, each with a distinctive structure factor indicating that they are nonetheless cooperative excitations. We interpret the overall structure of the spectrum as containing four branches, one hybridized with the phonons and gaining a strong dispersion, and three remaining dispersionless.

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., 9 pages, 4 figures

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.

Chemical science 9(14), 3555-3562 (2018). doi:10.1039/C8SC00163D, Published by RSC, Cambridge

In the Cr7Co model-system the anisotropy of CoII is effectively transferred to the whole cluster through strong and anisotropic exchange interactions., The Cr7Co ring represents a model system to understand how the anisotropy of a CoII ion is transferred to the effective anisotropy of a polymetallic cluster by strong exchange interactions. Combining sizeable anisotropy with exchange interactions is an important point in the understanding and design of new anisotropic molecular nanomagnets addressing fundamental and applicative issues. By combining electron paramagnetic resonance and inelastic neutron scattering measurements with spin Hamiltonian and ab initio calculations, we have investigated in detail the anisotropy of the CoII ion embedded in the antiferromagnetic ring. Our results demonstrate a strong and anisotropic exchange interaction between the Co and the neighbouring Cr ions, which effectively transmits the anisotropy to the whole molecule.

Correction for ‘Anisotropy of CoII transferred to the Cr7Co polymetallic cluster via strong exchange interactions’ by Elena Garlatti et al., Chem. Sci., 2018, DOI: ; 10.1039/c8sc00163d.

Total control over the electronic spin relaxation in molecular nanomagnets is the ultimate goal in the design of new molecules with evermore realizable applications in spin-based devices. For single-ion lanthanide systems, with strong spin-orbit coupling, the potential applications are linked to the energetic structure of the crystal field levels and quantum tunneling within the ground state. Structural engineering of the timescale of these tunneling events via appropriate design of crystal fields represents a fundamental challenge for the synthetic chemist, since tunnel splittings are expected to be suppressed by crystal field environments with sufficiently high-order symmetry. Here, we report the long missing study of the effect of a non-linear (C4) to pseudo-linear (D4d) change in crystal field symmetry in an otherwise chemically unaltered dysprosium complex. From a purely experimental study of crystal field levels and electronic spin dynamics at milliKelvin temperatures, we demonstrate the ensuing threefold reduction of the tunnel splitting., M.A.S., U.B.H., K.L., and J.Be. acknowledge financial support from the Danish Research Councils for Independent Research (12-125226). M.A.S., U.B.H., M.R, and K.L. acknowledge DANSCATT for financial support for the neutron scattering experiments. For the experiments conducted at FRM II, this project has received funding from the European Union’s 7th Framework Programme for research, technological development and demonstration under the NMI3-II Grant number 283883. M.A.S. thanks the Oticon Foundation (16-2669), and the Augustinus Foundation (16-2917) for financial support in relation to a research stay at Institut für Physikalische Chemie, Universität Stuttgart, Germany. M.P. and J.v.S. thank the DFG for funding (SL104/5-1). K.S.P. thanks the Danish Research Council for Independent Research for a DFF-Sapere Aude Research Talent grant (4090-00201). E.B., A.A, and, J.Ba. acknowledge the financial support of Spanish MINECO project MAT2017-83468-R. M.J. acknowledges the Swiss National Science Foundation.

The global zero-field splitting (ZFS) parameters of three, ferromagnetically coupled, μ3-κ3-[XO4]– (X = Cl, Re) capped, manganese(III) oximate single-molecule magnets, [Mn3O(R-sao)3(2,4′-bipyridine)3XO4] [X = Cl, R = Me, Et; X = Re, R = Me; Me-sao = 2-hydroxyphenylethanone oximate(2–)], with crystallographic trigonal symmetry were determined by use of inelastic neutron scattering and high-field/high-frequency electron paramagnetic resonance spectroscopy. ReO4– (O···O ca. 1.7 A) is larger than ClO4– (O···O ca. 1.4 A), which allows more parallel alignment of the local ZFS tensors. However, this chemical modification results in concomitant distortions in the equatorial ligand plane. Consistent parametrization of all spectroscopic data was achieved, and effective spin-reversal barriers determined from alternating current susceptibility data were shown to be in good accordance with the energy barriers deduced from spectroscopy.

The inelastic response of AV2Al20 (with A = Al, Ga and Y) was probed by high-resolution inelastic neutron scattering experiments and density functional theory (DFT) based lattice dynamics calculations (LDC). Features characteristic of the dynamics of Al, Ga and Y are established experimentally in the low-energy range of the compounds. In the stereotype 'Einstein-solid' compound AlV2Al20 we identify a unique spectral density extending up to 10 meV at 1.6 K. Its dominating feature is a peak centred at 2 meV at the base temperature. A very similar spectral distribution is established in GaV2Al20 albeit the strong peak is located at 1 meV at 1.6 K. In YV2Al20 signals characteristic of Y dynamics are located above 8 meV. The spectral distributions are reproduced by the DFT-based LDC and identified as a set of phonons. The response to temperature changes between 1.6 and ∼300 K is studied experimentally and the exceptionally vivid renormalization of the A characteristic modes in AlV2Al20 and GaV2Al20 is quantified by following the energy of the strong peak. At about 300 K it is shifted to higher energies by 300% for A = Al and 450% for A = Ga. The dynamics of A = Y in YV2Al20 show a minor temperature effect. This holds in general for modes located above 10 meV in any of the compounds. They are associated with vibrations of the V2Al20 matrix. Atomic potentials derived through DFT calculations indicate the propensity of A = Al and Ga to a strong positive energy shift upon temperature increase by a high quartic component. The effect of the strong phonon renormalization on thermodynamic observables is computed on grounds of the LDC results. It is shown that through the hybridization of A = Al and Ga with the V2Al20 dynamics the matrix vibrations in the low-energy range follow this renormalization.

CeCuAl

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 LaFePO0.9, they have not been observed by inelastic neutron scattering (INS). LaFePO0.9 is an iron-based superconductor with a low superconducting transition temperature (Tc = 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.

We explore the field-temperature phase diagram of the XY pyrochlore antiferromagnet ${\mathrm{Er}}_{2}{\mathrm{Ti}}_{2}{\mathrm{O}}_{7}$ by means of magnetization and neutron diffraction experiments. Depending on the field strength and direction relative to the high symmetry cubic directions $[001],[1\overline{1}0]$, and $[111]$, the refined field-induced magnetic structures are derived from the zero field ${\ensuremath{\psi}}_{2}$ and ${\ensuremath{\psi}}_{3}$ states of the ${\mathrm{\ensuremath{\Gamma}}}_{5}$ irreducible representation which describes the ground state of XY pyrochlore antiferromagnets. At low field, domain selection effects are systematically at play. In addition, for $[001]$, a phase transition is reported towards a ${\ensuremath{\psi}}_{3}$ structure at a characteristic field ${H}_{c}^{001}=43$ mT. For $[1\overline{1}0]$ and $[111]$, the spins are continuously tilted by the field from the ${\ensuremath{\psi}}_{2}$ state, and no phase transition is found while domain selection gives rise to sharp anomalies in the field dependence of the Bragg peaks intensity. For $[1\overline{1}0]$, these results are confirmed by high resolution inelastic neutron scattering experiments, which in addition allow us to determine the field dependence of the spin gap. This study agrees qualitatively with the scenario proposed theoretically by Maryasin et al. [Phys. Rev. B 93, 100406(R) (2016)], yet the strength of the field-induced anisotropies is significantly different from theory.

${\mathrm{CePd}}_{2}{\mathrm{Al}}_{2\ensuremath{-}x}{\mathrm{Ga}}_{x}$ compounds crystallizing in the tetragonal ${\mathrm{CaBe}}_{2}{\mathrm{Ge}}_{2}$-type structure (space group $P4/nmm$) and undergoing a structural phase transition to an orthorhombic structure ($Cmme$) at low temperatures were studied by means of neutron scattering. The amplitude-modulated magnetic structure of ${\mathrm{CePd}}_{2}{\mathrm{Al}}_{2}$ is described by an incommensurate propagation vector $\stackrel{P\vec}{k}=({\ensuremath{\delta}}_{x},\frac{1}{2}+{\ensuremath{\delta}}_{y},0)$ with ${\ensuremath{\delta}}_{x}=0.06$ and ${\ensuremath{\delta}}_{y}=0.04$. The magnetic moments order antiferromagnetically within the $ab$ planes stacked along the $c$ axis and are arranged along the direction close to the orthorhombic $a$ axis with a maximum value of 1.5(1) ${\ensuremath{\mu}}_{\mathrm{B}}/{\mathrm{Ce}}^{3+}$. ${\mathrm{CePd}}_{2}{\mathrm{Ga}}_{2}$ reveals a magnetic structure composed of two components: the first is described by the propagation vector $\stackrel{P\vec}{{k}_{1}}=(\frac{1}{2},\phantom{\rule{0.16em}{0ex}}\frac{1}{2},\phantom{\rule{0.16em}{0ex}}0)$, and the second one propagates with $\stackrel{P\vec}{{k}_{2}}=(0,\frac{1}{2},0)$. The magnetic moments of both components are aligned along the same direction---the orthorhombic [100] direction---and their total amplitude varies depending on the mutual phase of magnetic moment components on each Ce site. The propagation vectors $\stackrel{P\vec}{{k}_{1}}$ and $\stackrel{P\vec}{{k}_{2}}$ describe also the magnetic structure of substituted ${\mathrm{CePd}}_{2}{\mathrm{Al}}_{2\ensuremath{-}x}{\mathrm{Ga}}_{x}$ compounds, except the one with $x=0.1.\phantom{\rule{0.28em}{0ex}}{\mathrm{CePd}}_{2}{\mathrm{Al}}_{1.9}{\mathrm{Ga}}_{0.1}$ with magnetic structure described by $\stackrel{P\vec}{k}$ and $\stackrel{P\vec}{{k}_{1}}$ stays on the border between pure ${\mathrm{CePd}}_{2}{\mathrm{Al}}_{2}$ and the rest of the series. Determined magnetic structures are compared with other Ce 112 compounds. Inelastic neutron scattering experiments disclosed three nondispersive magnetic excitations in the paramagnetic state of ${\mathrm{CePd}}_{2}{\mathrm{Al}}_{2}$, while only two crystal field (CF) excitations are expected from the splitting of ground state $J=\frac{5}{2}$ of the ${\mathrm{Ce}}^{3+}$ ion in a tetragonal/orthorhombic point symmetry. Three magnetic excitations at 1.4, 7.8, and 15.9 meV are observed in the tetragonal phase of ${\mathrm{CePd}}_{2}{\mathrm{Al}}_{2}$. A structural phase transition to an orthorhombic structure shifts the first excitation up to 3.7 meV, while the other two excitations remain at almost the same energy. The presence of an additional magnetic peak is discussed and described within the Thalmeier-Fulde CF-phonon coupling (i.e., magnetoelastic coupling) model generalized to the tetragonal point symmetry. The second parent compound ${\mathrm{CePd}}_{2}{\mathrm{Ga}}_{2}$ does not display any sign of additional magnetic excitation. The expected two CF excitations were observed. The development of magnetic excitations in the ${\mathrm{CePd}}_{2}{\mathrm{Al}}_{2\ensuremath{-}x}{\mathrm{Ga}}_{x}$ series is discussed and crystal field parameters determined.

Compounds of general formula [Cr7MF3(Etglu)(O2C(t)Bu)15(Phpy)] [H5Etglu = N-ethyl-d-glucamine; Phpy = 4-phenylpyridine; M = Zn (1), Mn (2), Ni (3)] have been prepared. The structures contain an irregular octagon of metal sites formed around the penta-deprotonated Etglu(5-) ligand; the chirality of N-ethyl-d-glucamine is retained in the final product. The seven Cr(III) sites have a range of coordination environments, and the divalent metal site is crystallographically identified and has a Phpy ligand attached to it. By using complementary experimental techniques, including magnetization and specific heat measurements, inelastic neutron scattering, and electron paramagnetic resonance spectroscopy, we have investigated the magnetic features of this family of {Cr7M} rings. Microscopic parameters of the spin Hamiltonian have been determined as a result of best fits of the different experimental data, allowing a direct comparison with corresponding parameters found in the parent compounds. We examine whether these parameters can be transferred between compounds and compare them with those of an earlier family of heterometallic rings.

We report on the inelastic response of AV2Al20 (with A = Sc, La and Ce) probed by high-resolution inelastic neutron scattering experiments. Intense signals associated with the dynamics of Sc, La and Ce are identified in the low-energy range at 6–14 meV in ScV2Al20 and at 8–16 meV in LaV2Al20 and CeV2Al20. Their response to temperature changes between 2 and 300 K reveals a very weak softening of the modes upon heating in LaV2Al20 and CeV2Al20 and a distinguished blue shift by about 2 meV in ScV2Al20. By means of density functional theory (DFT) and lattice dynamics calculations (LDC) we show that the unusual anharmonicity of the Sc-dominated modes is due to the local potential of Sc featured by a strong quartic term. The vibrational dynamics of ScV2Al20 as well as of LaV2Al20 and CeV2Al20 is reproduced by a set of eigenmodes. To screen the validity of the DFT and LDC results they are confronted with data from X-ray diffraction measurements. The effect of the strong phonon renormalization in ScV2Al20 on thermodynamic observables is computed on grounds of the LDC derived inelastic response. To set the data in a general context of AV2Al20 compounds and their physical properties we report in addition computer and experimental results of the binary V2Al20 compound.

We study the ligand-field splittings and magnetic properties of three ErIII single-ion magnets which differ in the peripheral ligand sphere but exhibit similar first coordination spheres by inelastic neutron scattering (INS) and SQUID magnetometry. The INS spectra of the three compounds are profoundly different pointing at a strong response of the magnetic behavior to minor structural changes, as they are e.g. encountered when depositing molecules on surfaces. The observation of several magnetic excitations within the J = 15/2 ground multiplet together with single-crystal magnetic measurements allows for the extraction of the sign and magnitude of all symmetry-allowed Stevens parameters. The parameter values and the energy spectrum derived from INS are compared to the results of state-of-the-art ab initio CASSCF calculations. Temperature-dependent alternating current (ac) susceptibility measurements suggest that the magnetisation relaxation in the investigated temperature range of 1.9 K < T < 5 K is dominated by quantum tunnelling of magnetisation and two-phonon Raman processes. The possibility of observing electron paramagnetic resonance transitions between the ground-state doublet states, which can be suppressed in perfectly axial single-ion magnets, renders the studied systems interesting as representations of quantum bits., Chemical Science, 5 (4), ISSN:2041-6520, ISSN:2041-6539

This short overview gives an account on the use of neutron spectroscopy for the examination of molecular nanomagnets, systems constructed by crystalline arrangement of finite size clusters (usually with regular form) of interacting moment carrying atoms – magnetic molecules. Opposed to extended magnetic systems with bands of collective excitations such as spin-waves the molecular nanomagnets are entities with local properties, each magnetic molecule possessing a finite number of energy levels that can be solved exactly for small enough systems. In essence, the number of states remains finite despite growing rapidly with increasing number of magnetic centers and the value of the spin quantum number. Increasingly large numbers of states and more complex exchange networks lead to the need for approximative treatments, the validity of which can be checked with neutron spectroscopy. Molecular nanomagnets provide interesting examples of physics and magnetochemistry, illustrated here with a few examples that highlight the power of neutron spectroscopy for precise investigation of the energy level structure and spatial configuration of the magnetic exchange parameters.

The mononuclear complex (Bu

We present an experimental study of the quantum spin ice candidate pyrochlore compound ${\mathrm{Pr}}_{2}{\mathrm{Zr}}_{2}{\mathrm{O}}_{7}$ by means of magnetization measurements, specific heat, and neutron scattering up to 12 T and down to 60 mK. When the field is applied along the $[111]$ and $[1\overline{1}0]$ directions, $\mathbf{k}=0$ field-induced structures settle in. We find that the ordered moment rises slowly, even at very low temperature, in agreement with macroscopic magnetization. Interestingly, for $H\ensuremath{\parallel}[1\overline{1}0]$, the ordered moment appears on the so-called $\ensuremath{\alpha}$ chains only. The spin excitation spectrum is essentially inelastic and consists in a broad flat mode centered at about 0.4 meV with a magnetic structure factor which resembles the spin ice pattern. For $H\ensuremath{\parallel}[1\overline{1}0]$ (at least up to 2.5 T), we find that a well-defined mode forms from this broad response, whose energy increases with $H$, in the same way as the temperature of the specific-heat anomaly. We finally discuss these results in the light of mean field calculations and propose an interpretation where quadrupolar interactions play a major role, overcoming the magnetic exchange. In this picture, the spin ice pattern appears shifted up to finite energy because of those interactions. We then propose a range of acceptable parameters for ${\mathrm{Pr}}_{2}{\mathrm{Zr}}_{2}{\mathrm{O}}_{7}$ that allow to reproduce several experimental features observed under field. With these parameters, the actual ground state of this material would be an antiferroquadrupolar liquid with spin-ice-like excitations.

Fractionalised excitations that emerge from a many body system have revealed rich physics and concepts, from composite fermions in two-dimensional electron systems, revealed through the fractional quantum Hall effect, to spinons in antiferromagnetic chains and, more recently, fractionalisation of Dirac electrons in graphene and magnetic monopoles in spin ice. Even more surprising is the fragmentation of the degrees of freedom themselves, leading to coexisting and a priori independent ground states. This puzzling phenomenon was recently put forward in the context of spin ice, in which the magnetic moment field can fragment, resulting in a dual ground state consisting of a fluctuating spin liquid, a so-called Coulomb phase, on top of a magnetic monopole crystal. Here we show, by means of neutron scattering measurements, that such fragmentation occurs in the spin ice candidate Nd$_2$Zr$_2$O$_7$. We observe the spectacular coexistence of an antiferromagnetic order induced by the monopole crystallisation and a fluctuating state with ferromagnetic correlations. Experimentally, this fragmentation manifests itself via the superposition of magnetic Bragg peaks, characteristic of the ordered phase, and a pinch point pattern, characteristic of the Coulomb phase. These results highlight the relevance of the fragmentation concept to describe the physics of systems that are simultaneously ordered and fluctuating., Comment: accepted in Nature Physics

International audience; The mononuclear complex (Bu4N)2[ReIVCl4(CN)2].2DMA (DMA =N,N-dimethylacetamide) displays intricate magnetization dynamics, implying Orbach, direct, and Raman-type relaxation processes. The Orbach relaxation process is characterized by an energy barrier of 39 K (27 cm-1) that is discussed based on high-field electron paramagnetic resonance (EPR), inelastic neutron scattering and frequency domain THz EPR investigations.

The reaction of [MnIII(5-Brsalen)(MeOH)](ClO4) (5-Brsalen2 − = N,N′-ethylenebis(5-bromosalicylidene-iminate)) with [IrIII(CN)6]3 − yields a trinuclear, cyanide-bridged MnIII–IrIII–MnIII cluster which is a member of an isostructural series of MnIII–MIII–MnIII clusters. The presence of the large, diamagnetic [IrIII(CN)6]3 − bridging unit facilitates a precise determination of the MnIII zero-field splitting (zfs) parameters by the combined use of inelastic neutron scattering, high-field, high-frequency EPR spectroscopy and magnetic measurements. The single-ion axial (D) and rhombic (E) zfs parameters are found to be D = − 3.72(5) cm− 1 and |E| = 0.21(1) cm− 1. The experimental data are consistent with a small, antiferromagnetic exchange interaction between the two MnIII ions.

Molecular nanomagnets are among the first examples of finite-size spin systems and have been test beds for addressing several phenomena in quantum dynamics. In fact, for short-enough timescales the spin wavefunctions evolve coherently according to an appropriate spin Hamiltonian, which can be engineered to meet specific requirements. Unfortunately, so far it has been impossible to determine these spin dynamics directly. Here we show that recently developed instrumentation yields the four-dimensional inelastic-neutron scattering function in vast portions of reciprocal space and enables the spin dynamics to be determined directly. We use the Cr 8 antiferromagnetic ring as a benchmark to demonstrate the potential of this approach which allows us, for example, to examine how quantum fluctuations propagate along the ring or to test the degree of validity of the Néel-vector-tunnelling framework. © 2012 Macmillan Publishers Limited. All rights reserved.

We report on the synthesis, crystal structure and magnetic characterisation of the trinuclear, fluoride-bridged, molecular nanomagnet [Dy(hfac)(3)(H2O)-CrF2(py)(4)-Dy(hfac)(3)(NO3)] (1) (hfacH = 1,1,1,5,5,5-hexafluoroacetylacetone, py = pyridine) and a closely related dinuclear species [Dy(hfac)(4)-CrF2( py)(4)]center dot 1/2 CHCl3 (2). Element-specific magnetisation curves obtained on 1 by X-ray magnetic circular dichroism (XMCD) allow us to directly observe the field-induced transition from a ferrimagnetic to a ferromagnetic arrangement of the Dy and Cr magnetic moments. By fitting a spin-Hamiltonian model to the XMCD data we extract a weak antiferromagnetic exchange coupling of j -0.18 cm(-1) between the Dy-III and Cr-III ions. The value found from XMCD is consistent with SQUID magnetometry and inelastic neutron scattering measurements. Furthermore, alternating current susceptibility and muon-spin relaxation measurements reveal that 1 shows thermally activated relaxation of magnetisation with a small effective barrier for magnetisation reversal of Delta(eff) 3 cm(-1). Density-functional theory calculations show that the Dy-Cr couplings originate from superexchange via the fluoride bridges.

We have investigated the novel single-molecule magnet (NEt(4))[Mn(2)(5-Brsalen)(2)(MeOH)(2)Cr(CN)(6)] (1; 5-Brsalen = N,N'-ethylenebis(5-bromosalicylidene)iminato anion) using spectroscopic as well as magnetization and susceptibility measurements. Frequency-domain Fourier-transform terahertz electron paramagnetic resonance (FDFT THz-EPR) based on the generation of THz radiation from a synchrotron in combination with inelastic neutron scattering (INS) allows for the discrimination between intermultiplet and intramultiplet transitions. Together with ac/dc magnetic susceptibility measurements the obtained set of data provides a complete characterization of the lowest energetic magnetic excitations. We find that the new compound 1 exhibits much weaker intermolecular interactions than found in the closely related compound: K[Mn(2)(5-Brsalen)(2)(H(2)O)(2)Cr(CN)(6)] (2). Furthermore, two phonon lines in the vicinity of the magnetic excitations are detected.

We report the first single-molecule magnet (SMM) to incorporate the [Os(CN)(6)](3-) moiety. The compound (1) has a trimeric, cyanide-bridged Mn(III)-Os(III)-Mn(III) skeleton in which Mn(III) designates a [Mn(5-Brsalen)(MeOH)](+) unit (5-Brsalen=N,N'-ethylenebis(5-bromosalicylideneiminato)). X-ray crystallographic experiments reveal that 1 is isostructural with the Mn(III)-Fe(III)-Mn(III) analogue (2). Both compounds exhibit a frequency-dependent out-of-phase χ''(T) alternating current (ac) susceptibility signal that is suggestive of SMM behaviour. From the Arrhenius expression, the effective barrier for 1 is found to be Δ(eff)/k(B)=19 K (τ(0)=5.0×10(-7) s; k(B)=Boltzmann constant), whereas only the onset (1.5 kHz, 1.8 K) of χ''(T) is observed for 2, thus indicating a higher blocking temperature for 1. The strong spin-orbit coupling present in Os(III) isolates the E'(1g(1/2))(O(h)*) Kramers doublet that exhibits orbital contributions to the single-ion anisotropy. Magnetic susceptibility and inelastic neutron-scattering measurements reveal that substitution of [Fe(CN)(6)](3-) by the [Os(CN)(6)](3-) anion results in larger ferromagnetic, anisotropic exchange interactions going from quasi-Ising exchange interactions in 2 to pure Ising exchange for 1 with J(parallel)(MnOs)=-30.6 cm(-1). The combination of diffuse magnetic orbitals and the Ising-type exchange interaction effectively contributes to a higher blocking temperature. This result is in accordance with theoretical predictions and paves the way for the design of a new generation of SMMs with enhanced SMM properties.

The ILL instrument IN5 was constructed in the 1970s after a proposed outline from Reinhard Scherm and coworkers in 1967 [1]. Apart from some technical improvements about once a decade–for example on the chopper system and the completion of the detector area in 1988–the basic instrument remained almost unchanged for more than 30 years. In 1996, it was decided to refurbish the primary spectrometer–upstream from the sample–with a super-mirror focusing guide and an optimized counter-rotating disks chopper system. Started in 1998 this project was completed by the end of 2002, and the instrument welcomed its first users in spring 2003. A further step for a full refurbishment of this instrument was started in 2004, with the objective to improve the secondary spectrometer. The upgrade was run in parallel with the instrument user operation.

The tetrameric Ni(II) spin cluster Ni4Mo12 has been studied by INS. The data were analyzed extensively in terms of a very general spin Hamiltonian, which includes antiferromagnetic Heisenberg interactions, biquadratic 2-spin and 3-spin interactions, a single-ion magnetic anisotropy, and Dzyaloshinsky-Moriya interactions. Some of the experimentally observed features in the INS spectra could be reproduced, however, one feature at 1.65 meV resisted all efforts. This supports the conclusion that the spin Hamiltonian approach is not adequate to describe the magnetism in Ni4Mo12. The isotropic terms in the spin Hamiltonian can be obtained in a strong-coupling expansion of the Hubbard model at half-filling. Therefore detailed theoretical studies of the Hubbard model were undertaken, using analytical as well as numerical techniques. We carefully analyzed its abilities and restrictions in applications to molecular spin clusters. As a main result it was found that the Hubbard model is also unable to appropriately explain the magnetism in Ni4Mo12. Extensions of the model are also discussed., 12 pages, 12 figures

In the present article, we proffer an explanation for the origin of single molecule magnetism in [CuIILTbIII(hfac)2]2, a member of the novel class of mixed transition−lanthanide metal clusters. The theoretical model takes into account the crystal field acting on the TbIII ion as well as the exchange interaction between the TbIII and CuII ions and provides a good account of the low-lying energy levels, rigorously measured by inelastic neutron scattering and magnetic data. We demonstate that the single molecule magnet (SMM) behavior is not a sole consequence of the low-lying levels of the lanthanide metal ion but a property of the tetranuclear cluster itself. The energy levels are shown to increase with the decrease of the mean value of the Z-projection of the total angular momentum of the cluster, thus forming a barrier for magnetization reversal that is wholly consistent with the observed SMM behavior. On the basis of this study, recommendations are formulated on how the SMM properties for nd−4f clusters ...

The electronic structures of the compounds K[(5-Brsalen)2(H2O)2-Mn2MIII(CN)6]·2H2O (MIII = CoIII, CrIII, FeIII) have been determined by inelastic neutron scattering (INS) and magnetic susceptibility studies, revealing the manganese(III) single-ion anisotropy and exchange interactions that define the low-lying states of the Mn−MIII−Mn trimeric units. Despite the presence of an antiferromagnetic intertrimer interaction, the experimental evidence supports the classification of both the Cr(III) and Fe(III) compounds as single-molecule magnets. The value of 17(2) cm−1 established from AC susceptibility measurements for a spin-reversal barrier of K[(5-Brsalen)2(H2O)2-Mn2Cr(CN)6]·2H2O may be readily rationalized in terms of the energy level diagram determined directly by INS. AC susceptibility measurements on samples of K[(5-Brsalen)2(H2O)2-Mn2Fe(CN)6]·2H2O are contrary to those previously reported, exhibiting but the onset of peaks below temperatures of 1.8 K at oscillating frequencies in the range of 100−800 H...

We report the synthesis and structural characterisation of a family of finite molecular chains, specifically [{[R2NH2](3) [Cr6F11 (O2CCMe3)(10)]}(2)] (in which R=nPr 1, Et 2, nBu 3), [{Et2NH}(2) {[Et2NH2](3)[Cr7F12(O2C-CMe3)(12)][HO2CCMe3](2)}(2)] (4), [{[Me2NH2](3)[Cr6F11(O2CCMe3)(10)]center dot 2.5 H2O}(4)] (5) and [I{iPr(2)NH(2)](3)[Cr7F12(O2CCMe3)(12)]}(2)] (6). The structures all contain horseshoes of chromium centres, with each Cr center dot center dot center dot Cr contact within the horseshoe bridged by a fluoride and two pivalates. The horseshoes are linked through hydrogen bonds to the secondary ammonium cations in the structure, leading to di- and tetrahorseshoe structures. Through magnetic measurements and inelastic neutron scattering studies we have determined the exchange coupling constants in 1 and 6. In 1 it is possible to distinguish two exchange interactions, J(A) = -1.1 meV and J(B) = -1.4 meV; J(A) is the exchange interactions at the tips of the horseshoe and JB is the exchange within the body of the horseshoe (1 meV = 8.066 cm(-1)). For 6 only one interaction was needed to model the data: J=-1.18meV The single-ion anisotropy parameters for Cr-III were also derived for the two compounds as: for 1, D-Cr = -0.028 meV and vertical bar ECr vertical bar = 0.005meV; for 6, D-Cr=-0.031meV. Magnetic-field-dependent inelastic neutron scattering experiments on I allowed the Zeeman splitting of the first two excited states and level crossings to be observed. For the tetramer of horseshoes (5), quantum Monte Carlo calculations were used to fit the magnetic susceptibility behaviour, giving two exchange interactions within the horseshoe (-1.32 and -1.65 meV) and a weak inter-horseshoe coupling of +0.12meV. Multi-frequency variable-temperature EPR studies on 1, 2 and 6 have also been performed, allowing further characterisation of the spin Hamiltonian parameters of these chains.

Determination of the electronic energy spectrum of a trigonalsymtnetry mononuclear Yb3+ single-molecule magnet (SMM) by highresolution absorption and luniinescente spectroscopies reveals that the first excited electronic doublet is placed nearly 500 cm(-1) above the ground one. Fitting of the paramagnetic relaxation times of this- SMM to a thermally activated (Orbach) model {tau = tau(0) X exp [Delta(Orbach)/(k(B)T)]} affords an activation barrier, Delta(Orbach), of only 38 cm(-1). This result is incompatible with the spectroscopic observations. Thus, we unambiguously demonstrate, solely on the basis Of experimental data, that Orbach relaxation cannot ci priori be considered as the main mechanism determining the spin dynamics of SM.Ms. This study highlights the fact that the general:synthetic approach of optimizing SMM behavior by maximization of the anisotropy barrier, intimately linked to the ligand field, 'as the sole paratneter to be tuned, is insufficient because of the complete neglect of the interaction of the magnetic moment of the molecule with its environment. The Orbach mechanism is expected dominant only in the cases in which the energy of the excited ligand field state is below the Debye temperature, which is typically low for molecular crystals and, thus, prevents the use of the anisotropy barrier as a design criterion, for the realization of high-temperature SM.Ms. Therefcire, consideration of additional design criteria that address the presence of alternative relaxation processes beyond the traditional double-well picture is required.

A magnetic insulator, LiInCr${}_{4}$O${}_{8}$ realizes a so-called ``breathing'' pyrochlore lattice of $S=3/2$ spins on corner-sharing tetrahedra that alternate in size. In this manuscript, a collaboration of researchers from Institut Laue-Langevin in Grenoble and Institute for Solid State Physics in Tokyo present a detailed neutron scattering study that elucidates the sequence of structural and magnetic phase transitions that occur at low temperatures in this material.

We report the results of neutron diffraction and inelastic neutron scattering on a powder sample of Gd_{3}Ga_{5}O_{12} at high magnetic fields. Analysis of the diffraction data shows that in high fields (B≳1.8 T) the spins are not fully aligned, but are canted slightly as a result of the dipolar interaction. The magnetic phase for fields ≲1.8 T is characterized by antiferromagnetic peaks at (210) and an incommensurate wave vector. The dominant contribution to inelastic scattering at large momentum transfers is from a band of almost dispersionless excitations. We show that these correspond to the spin waves localized on ten site rings, expected on the basis of nearest neighbor exchange interaction, and that the spectrum at high fields B≳1.8 T is well described by a spin wave theory.

A new family of tetranuclear Ni complexes [Ni(4)(ROH)(4)L(4)] (H(2)L = salicylidene-2-ethanolamine; R = Me (1) or Et (2)) has been synthesized and studied. Complexes 1 and 2 possess a [Ni(4)O(4)] core comprising a distorted cubane arrangement. Magnetic susceptibility and inelastic neutron scattering studies indicate a combination of ferromagnetic and antiferromagnetic pairwise exchange interactions between the four Ni(II) centers, resulting in an S = 4 spin ground state. Magnetization measurements reveal an easy-axis-type magnetic anisotropy with D approximately -0.93 cm(-)(1) for both complexes. Despite the large magnetic anisotropy, no slow relaxation of the magnetization is observed down to 40 mK. To determine the origin of the low-temperature magnetic behavior, the magnetic anisotropy of complex 1 was probed in detail using inelastic neutron scattering and frequency domain magnetic resonance spectroscopy. The spectroscopic studies confirm the easy-axis-type anisotropy and indicate strong transverse interactions. These lead to rapid quantum tunneling of the magnetization, explaining the unexpected absence of slow magnetization relaxation for complex 1.

The low-temperature properties of a diluted antiferromagnetic pyrochlore slab of S = 3/2 spins are investigated through a study of the frustrated oxides Ba 2 Sn 2 Ga 10-7p ZnCr 7p O 22 (p > 0.85). Powder neutron diffraction and 119 Sn Mossbauer absorption show no evidence of long-range magnetic order above 1.5 K. As in SrCr 9q Ga 12-9q O 19 , diffuse magnetic scattering, indicative of short range spin-spin correlations, is observed at low temperature. The dependence of the low-temperature sub-Curie bulk susceptibility to weak site depletion is the inverse of that observed in SrCr 9q Ga 12-9q O 19 .