Low-energy magnons in the chiral ferrimagnet Cu2OSeO3: A coarse-grained approach.

We report a comprehensive neutron scattering study of low energy magnetic excitations in the breathing pyrochlore helimagnetic Cu2OSeO3. Fully documenting the four lowest energy magnetic modes that leave the ferrimagnetic configuration of the "strong tetrahedra" intact ( | ℏ ω | < 13 meV), we find gapless quadratic dispersion at the point for energies above 0.2 meV, two doublets separated by 1.6(2) meV at the R point, and a bounded continuum at the X point. Our constrained rigid spin cluster model relates these features to Dzyaloshinskii-Moriya (DM) interactions and the incommensurate helical ground state. Combining conventional spin wave theory with a spin cluster form factor accurately reproduces the measured equal time structure factor through multiple Brillouin zones. An effective spin Hamiltonian describing complex anisotropic intercluster interactions is obtained.

Incommensurate Magnetism Near Quantum Criticality in CeNiAsO.

We report the discovery of incommensurate magnetism near quantum criticality in CeNiAsO through neutron scattering and zero field muon spin rotation. For T

Electron Doping of Proposed Kagome Quantum Spin Liquid Produces Localized States in the Band Gap.

Carrier doping of quantum spin liquids is a long-proposed route to the emergence of high-temperature superconductivity. Electrochemical intercalation in kagome hydroxyl halide materials shows that samples remain insulating across a wide range of electron counts. Here we demonstrate through first-principles density-functional calculations, corrected for self-interaction, the mechanism by which electrons remain localized in various Zn-Cu hydroxyl halides, independent of the chemical identity of the dopant-the formation of polaronic states with attendant lattice displacements and a dramatic narrowing of bandwidth upon electron addition. The same theoretical method applied to electron doping in cuprate Nd_{2}CuO_{4} correctly produces a metallic state when the initially formed polaron dissolves into an extended state. Our general findings explain the insulating behavior in a wide range of "doped" quantum magnets and demonstrate that new quantum spin liquid host materials are needed to realize metallicity borne of a spin liquid.

Universal geometric frustration in pyrochlores.

Materials with the pyrochlore/fluorite structure have diverse technological applications, from magnetism to nuclear waste disposal. Here we report the observation of structural instability present in the pyrochlores A2Zr2O6O' (A = Pr, La) and Yb2Ti2O6O', that exists despite ideal stoichiometry, ideal cation-ordering, the absence of lone pair effects, and a lack of magnetic order. Though these materials appear to have good long-range order, local structure probes find displacements, of the order of 0.01 nm, within the pyrochlore framework. The pattern of displacements of the A2O' sublattice mimics the entropically-driven fluxional motions characteristic of and well-known in the silica mineral ß-cristobalite. The universality of such displacements within the pyrochlore structure adds to the known structural diversity and explains the extreme sensitivity to composition found in quantum spin ices and the lack of ferroelectric behavior in pyrochlores.

Screened moments and extrinsic in-gap states in samarium hexaboride.

Samarium hexaboride (SmB6) is a Kondo insulator, with a narrow gap due to hybridization between localized and conduction electrons. Despite being an insulator, many samples show metal-like properties. Rare-earth purification is exceedingly difficult, and nominally pure samples may contain 2% or more of impurities. Here to determine the effects of rare-earth doping on SmB6, we synthesized and probed a series of gadolinium-doped samples. We found a relationship between specific heat and impurity moment screening which scales systematically. Consistent with this finding, our neutron scattering experiments of a high purity sample of doubly isotopic 154Sm11B6 show no intrinsic excitations below the well-established 13 meV spin-exciton. The result of introducing impurities into a Kondo insulator is incompletely understood, but it is clear from our measurements that there is a systematic relationship between rare-earth impurities and metal-like properties in SmB6.

Disordered Route to the Coulomb Quantum Spin Liquid: Random Transverse Fields on Spin Ice in Pr_{2}Zr_{2}O_{7}.

Inelastic neutron scattering reveals a broad continuum of excitations in Pr_{2}Zr_{2}O_{7}, the temperature and magnetic field dependence of which indicate a continuous distribution of quenched transverse fields (Δ) acting on the non-Kramers Pr^{3+} crystal field ground state doublets. Spin-ice correlations are apparent within 0.2 meV of the Zeeman energy. A random phase approximation provides an excellent account of the data with a transverse field distribution ρ(Δ)∝(Δ^{2}+Γ^{2})^{-1}, where Γ=0.27(1) meV. Established during high temperature synthesis due to an underlying structural instability, it appears disorder in Pr_{2}Zr_{2}O_{7} actually induces a quantum spin liquid.

NaSrMn2F7, NaCaFe2F7, and NaSrFe2F7: novel single crystal pyrochlore antiferromagnets.

The crystal structures and magnetic properties of three previously unreported A2B2F7 pyrochlore materials, NaSrMn2F7, NaCaFe2F7, and NaSrFe2F7 are presented. In these compounds, either S = 2Fe2+ or S = 5/2Mn2+ is on the B site, while nonmagnetic Na and Ca (Na and Sr) are disordered on the A site. The materials, which were grown as crystals via the floating zone method, display high effective magnetic moments and large Curie-Weiss thetas. Despite these characteristics, no ordering transition is detected. However, freezing of the magnetic spins, characterized by peaks in the susceptibility or specific heat, is observed at very low temperatures. The empirical frustration index, f = -θ CW/T f, for the materials are 36 (NaSrMn2F7), 27 (NaSrFe2F7), and 19 (NaCaFe2F7). AC susceptibility, DC susceptibility, and heat capacity measurements are used to characterize the observed spin glass behavior. The results suggest that the compounds are frustrated pyrochlore antiferromagnets with weak bond disorder. The magnetic phenomena that these fluoride pyrochlores exhibit, in addition to their availability as relatively large single crystals, make them promising candidates for the study of geometric magnetic frustration.

On the Chemistry and Physical Properties of Flux and Floating Zone Grown SmB6 Single Crystals.

Recent theoretical and experimental findings suggest the long-known but not well understood low temperature resistance plateau of SmB6 may originate from protected surface states arising from a topologically non-trivial bulk band structure having strong Kondo hybridization. Yet others have ascribed this feature to impurities, vacancies, and surface reconstructions. Given the typical methods used to prepare SmB6 single crystals, flux and floating-zone procedures, such ascriptions should not be taken lightly. We demonstrate how compositional variations and/or observable amounts of impurities in SmB6 crystals grown using both procedures affect the physical properties. From X-ray diffraction, neutron diffraction, and X-ray computed tomography experiments we observe that natural isotope containing (SmB6) and doubly isotope enriched ((154)Sm(11)B6) crystals prepared using aluminum flux contain co-crystallized, epitaxial aluminum. Further, a large, nearly stoichiometric crystal of SmB6 was successfully grown using the float-zone technique; upon continuing the zone melting, samarium vacancies were introduced. These samarium vacancies drastically alter the resistance and plateauing magnitude of the low temperature resistance compared to stoichiometric SmB6. These results highlight that impurities and compositional variations, even at low concentrations, must be considered when collecting/analyzing physical property data of SmB6. Finally, a more accurate samarium-154 coherent neutron scattering length, 8.9(1) fm, is reported.

Direct assignment of molecular vibrations via normal mode analysis of the neutron dynamic pair distribution function technique.

For over a century, vibrational spectroscopy has enhanced the study of materials. Yet, assignment of particular molecular motions to vibrational excitations has relied on indirect methods. Here, we demonstrate that applying group theoretical methods to the dynamic pair distribution function analysis of neutron scattering data provides direct access to the individual atomic displacements responsible for these excitations. Applied to the molecule-based frustrated magnet with a potential magnetic valence-bond state, LiZn2Mo3O8, this approach allows direct assignment of the constrained rotational mode of Mo3O13 clusters and internal modes of MoO6 polyhedra. We anticipate that coupling this well known data analysis technique with dynamic pair distribution function analysis will have broad application in connecting structural dynamics to physical properties in a wide range of molecular and solid state systems.

Block Magnetic Excitations in the Orbitally Selective Mott Insulator BaFe_{2}Se_{3}.

Iron pnictides and selenides display a variety of unusual magnetic phases originating from the interplay between electronic, orbital, and lattice degrees of freedom. Using powder inelastic neutron scattering on the two-leg ladder BaFe_{2}Se_{3}, we fully characterize the static and dynamic spin correlations associated with the Fe_{4} block state, an exotic magnetic ground state observed in this low-dimensional magnet and in Rb_{0.89}Fe_{1.58}Se_{2}. All the magnetic excitations of the Fe_{4} block state predicted by an effective Heisenberg model with localized spins are observed below 300 meV and quantitatively reproduced. However, the data only account for 16(3)µ_{B}^{2} per Fe^{2+}, approximatively 2/3 of the total spectral weight expected for localized S=2 moments. Our results highlight how orbital degrees of freedom in iron-based magnets can conspire to stabilize an exotic magnetic state.

Heat capacity peak at the quantum critical point of the transverse Ising magnet CoNb2O6.

The transverse Ising magnet Hamiltonian describing the Ising chain in a transverse magnetic field is the archetypal example of a system that undergoes a transition at a quantum critical point (QCP). The columbite CoNb2O6 is the closest realization of the transverse Ising magnet found to date. At low temperatures, neutron diffraction has observed a set of discrete collective spin modes near the QCP. Here, we ask if there are low-lying spin excitations distinct from these relatively high-energy modes. Using the heat capacity, we show that a significant band of gapless spin excitations exists. At the QCP, their spin entropy rises to a prominent peak that accounts for 30% of the total spin degrees of freedom. In a narrow field interval below the QCP, the gapless excitations display a fermion-like, temperature-linear heat capacity below 1 K. These novel gapless modes are the main spin excitations participating in, and affected by, the quantum transition.

Interaction driven subgap spin exciton in the Kondo insulator SmB6.

Using inelastic neutron scattering, we map a 14 meV coherent resonant mode in the topological Kondo insulator SmB6 and describe its relation to the low energy insulating band structure. The resonant intensity is confined to the X and R high symmetry points, repeating outside the first Brillouin zone and dispersing less than 2 meV, with a 5d-like magnetic form factor. We present a slave-boson treatment of the Anderson Hamiltonian with a third neighbor dominated hybridized band structure. This approach produces a spin exciton below the charge gap with features that are consistent with the observed neutron scattering. We find that maxima in the wave vector dependence of the inelastic neutron scattering indicate band inversion.

Ultrafast X-ray probing of water structure below the homogeneous ice nucleation temperature.

Water has a number of anomalous physical properties, and some of these become drastically enhanced on supercooling below the freezing point. Particular interest has focused on thermodynamic response functions that can be described using a normal component and an anomalous component that seems to diverge at about 228 kelvin (refs 1-3). This has prompted debate about conflicting theories that aim to explain many of the anomalous thermodynamic properties of water. One popular theory attributes the divergence to a phase transition between two forms of liquid water occurring in the 'no man's land' that lies below the homogeneous ice nucleation temperature (TH) at approximately 232 kelvin and above about 160 kelvin, and where rapid ice crystallization has prevented any measurements of the bulk liquid phase. In fact, the reliable determination of the structure of liquid water typically requires temperatures above about 250 kelvin. Water crystallization has been inhibited by using nanoconfinement, nanodroplets and association with biomolecules to give liquid samples at temperatures below TH, but such measurements rely on nanoscopic volumes of water where the interaction with the confining surfaces makes the relevance to bulk water unclear. Here we demonstrate that femtosecond X-ray laser pulses can be used to probe the structure of liquid water in micrometre-sized droplets that have been evaporatively cooled below TH. We find experimental evidence for the existence of metastable bulk liquid water down to temperatures of 227(-1)(+2) kelvin in the previously largely unexplored no man's land. We observe a continuous and accelerating increase in structural ordering on supercooling to approximately 229 kelvin, where the number of droplets containing ice crystals increases rapidly. But a few droplets remain liquid for about a millisecond even at this temperature. The hope now is that these observations and our detailed structural data will help identify those theories that best describe and explain the behaviour of water.

Hierarchy of bound states in the one-dimensional ferromagnetic Ising chain CoNb2O6 investigated by high-resolution time-domain terahertz spectroscopy.

Kink bound states in the one-dimensional ferromagnetic Ising chain compound CoNb2O6 have been studied using high-resolution time-domain terahertz spectroscopy in zero applied magnetic field. When magnetic order develops at low temperature, nine bound states of kinks become visible. Their energies can be modeled exceedingly well by the Airy function solutions to a 1D Schrödinger equation with a linear confining potential. This sequence of bound states terminates at a threshold energy near 2 times the energy of the lowest bound state. Above this energy scale we observe a broad feature consistent with the onset of the two particle continuum. At energies just below this threshold we observe a prominent excitation that we interpret as a novel bound state of bound states--two pairs of kinks on neighboring chains.

Evidence for topologically protected surface states and a superconducting phase in [Tl4](Tl(1-x)Sn(x))Te3 using photoemission, specific heat, and magnetization measurements, and density functional theory.

We report the discovery of surface states in the perovskite superconductor [Tl4]TlTe3 (Tl5Te3) and its nonsuperconducting tin-doped derivative [Tl4](Tl0.4Sn0.6)Te3 as observed by angle-resolved photoemission spectroscopy. Density functional theory calculations predict that the surface states are protected by a Z2 topology of the bulk band structure. Specific heat and magnetization measurements show that Tl5Te3 has a superconducting volume fraction in excess of 95%. Thus Tl5Te3 is an ideal material in which to study the interplay of bulk band topology and superconductivity.

Molecular quantum magnetism in LiZn2Mo3O8.

Inelastic neutron scattering at low temperatures T≤30 K from a powder of LiZn2Mo3O8 demonstrates this triangular-lattice antiferromagnet hosts collective magnetic excitations from spin-1/2 Mo3O13 molecules. Apparently gapless (Δ<0.2 meV) and extending at least up to 2.5 meV, the low-energy magnetic scattering cross section is surprisingly broad in momentum space and involves one-third of the spins present above 100 K. The data are compatible with the presence of valence bonds involving nearest-neighbor and next-nearest-neighbor spins forming a disordered or dynamic state.

HDAC inhibition by SNDX-275 (Entinostat) restores expression of silenced leukemia-associated transcription factors Nur77 and Nor1 and of key pro-apoptotic proteins in AML.

Nur77 and Nor1 are highly conserved orphan nuclear receptors. We have recently reported that nur77(-/-)nor1(-/-) mice rapidly develop acute myeloid leukemia (AML) and that Nur77 and Nor1 transcripts were universally downregulated in human AML blasts. These findings indicate that Nur77 and Nor1 function as leukemia suppressors. We further demonstrated silencing of Nur77 and Nor1 in leukemia stem cells (LSCs). We here report that inhibition of histone deacetylase (HDAC) using the specific class I HDAC inhibitor SNDX-275 restored the expression of Nur77/Nor1 and induced expression of activator protein 1 transcription factors c-Jun and JunB, and of death receptor TRAIL, in AML cells and in CD34(+)/38(-) AML LSCs. Importantly, SNDX-275 induced extensive apoptosis in AML cells, which could be suppressed by silencing nur77 and nor1. In addition, pro-apoptotic proteins Bim and Noxa were transcriptionally upregulated by SNDX-275 in AML cells and in LSCs. Our present work is the first report of a novel mechanism of HDAC inhibitor-induced apoptosis in AML that involves restoration of the silenced nuclear receptors Nur77 and Nor1, activation of activator protein 1 transcription factors, a death receptor and pro-apoptotic proteins.

Possible valence-bond condensation in the frustrated cluster magnet LiZn2Mo3O8.

The emergence of complex electronic behaviour from simple ingredients has resulted in the discovery of numerous states of matter. Many examples are found in systems exhibiting geometric magnetic frustration, which prevents simultaneous satisfaction of all magnetic interactions. This frustration gives rise to complex magnetic properties such as chiral spin structures, orbitally driven magnetism, spin-ice behaviour exhibiting Dirac strings with magnetic monopoles, valence-bond solids and spin liquids. Here we report the synthesis and characterization of LiZn(2)Mo(3)O(8), a geometrically frustrated antiferromagnet in which the magnetic moments are localized on small transition-metal clusters rather than individual ions. By doing so, first-order Jahn-Teller instabilities and orbital ordering are prevented, allowing the strongly interacting magnetic clusters in LiZn(2)Mo(3)O(8) to probably give rise to an exotic condensed valence-bond ground state reminiscent of the proposed resonating valence-bond state. Our results also link magnetism on clusters to geometric magnetic frustration in extended solids, demonstrating a new approach for unparalleled chemical control and tunability in the search for collective, emergent electronic states of matter.

MEK inhibition enhances ABT-737-induced leukemia cell apoptosis via prevention of ERK-activated MCL-1 induction and modulation of MCL-1/BIM complex.

Recently, strategies for acute myeloid leukemia (AML) therapy have been developed that target anti-apoptotic BCL2 family members using BH3-mimetic drugs such as ABT-737. Though effective against BCL2 and BCL-X(L), ABT-737 poorly inhibits MCL-1. Here we report that, unexpectedly, ABT-737 induces activation of the extracellular receptor activated kinase and induction of MCL-1 in AML cells. MEK inhibitors such as PD0325901 and CI-1040 have been used successfully to suppress MCL-1. We report that PD0325901 blocked ABT-737-induced MCL-1 expression, and when combined with ABT-737 resulted in potent synergistic killing of AML-derived cell lines, primary AML blast and CD34+38-123+ progenitor/stem cells. Finally, we tested the combination of ABT-737 and CI-1040 in a murine xenograft model using MOLM-13 human leukemia cells.Whereas control mice and CI-1040-treated mice exhibited progressive leukemia growth, ABT-737, and to a significantly greater extent, ABT-737+CI-1040 exerted major anti-leukemia activity. Collectively, results demonstrated unexpected anti-apoptotic interaction between the BCL2 family-targeted BH3-mimetic ABT-737 and mitogen-activated protein kinase signaling in AML cells: the BH3 mimetic is not only restrained in its activity by MCL-1, but also induces its expression. However, concomitant inhibition by BH3 mimetics and MEK inhibitors could abrogate this effect and may be developed into a novel and effective therapeutic strategy for patients with AML.

Wide-angle X-ray diffraction and molecular dynamics study of medium-range order in ambient and hot water.

We have developed wide-angle X-ray diffraction measurements with high energy-resolution and accuracy to study water structure at three different temperatures (7, 25 and 66 °C) under normal pressure. Using a spherically curved Ge crystal an energy resolution better than 15 eV has been achieved which eliminates influence from Compton scattering. The high quality of the data allows for a reliable Fourier transform of the experimental data resolving shell structure out to ~12 Å, i.e. 5 hydration shells. Large-scale molecular dynamics (MD) simulations using the TIP4P/2005 force-field reproduce excellently the experimental shell-structure in the range 4-12 Å although less agreement is seen for the first peak in the intermolecular pair-correlation function (PCF). The Shiratani-Sasai Local Structure Index [J. Chem. Phys. 104, 7671 (1996)] identifies a tetrahedral minority giving the intermediate-range oscillations in the O-O PCF and a disordered majority providing a more featureless background in this range. The current study supports the proposal that the structure of liquid water, even at high temperatures, can be described in terms of a two-state fluctuation model involving local structures related to the high-density and low-density forms of liquid water postulated in the liquid-liquid phase transition hypothesis.