Structure, Spin Correlations, and Magnetism of the S = 1/2 Square-Lattice Antiferromagnet Sr2CuTe1-xWxO6 (0 ≤ x ≤ 1).

Quantum spin liquids are highly entangled magnetic states with exotic properties. The S = 1/2 square-lattice Heisenberg model is one of the foundational models in frustrated magnetism with a predicted, but never observed, quantum spin liquid state. Isostructural double perovskites Sr2CuTeO6 and Sr2CuWO6 are physical realizations of this model but have distinctly different types of magnetic order and interactions due to a d10/d0 effect. Long-range magnetic order is suppressed in the solid solution Sr2CuTe1-xWxO6 in a wide region of x = 0.05-0.6, where the ground state has been proposed to be a disorder-induced spin liquid. Here, we present a comprehensive neutron scattering study of this system. We show using polarized neutron scattering that the spin liquid-like x = 0.2 and x = 0.5 samples have distinctly different local spin correlations, which suggests that they have different ground states. Low-temperature neutron diffraction measurements of the magnetically ordered W-rich samples reveal magnetic phase separation, which suggests that the previously ignored interlayer coupling between the square planes plays a role in the suppression of magnetic order at x ≈ 0.6. These results highlight the complex magnetism of Sr2CuTe1-xWxO6 and hint at a new quantum critical point between 0.2 < x < 0.4.

Dynamics in the ordered and disordered phases of barocaloric adamantane.

High-entropy order-disorder phase transitions can be used for efficient and eco-friendly barocaloric solid-state cooling. Here the barocaloric effect is reported in an archetypal plastic crystal, adamantane. Adamantane has a colossal isothermally reversible entropy change of 106 J K-1 kg-1. Extremely low hysteresis means that this can be accessed at pressure differences less than 200 bar. Configurational entropy can only account for about 40% of the total entropy change; the remainder is due to vibrational effects. Using neutron spectroscopy and supercell lattice dynamics calculations, it is found that this vibrational entropy change is mainly caused by softening in the high-entropy phase of acoustic modes that correspond to molecular rotations. We attribute this difference in the dynamics to the contrast between an 'interlocked' state in the low-entropy phase and sphere-like behaviour in the high-entropy phase. Although adamantane is a simple van der Waals solid with near-spherical molecules, this approach can be leveraged for the design of more complex barocaloric molecular crystals. Moreover, this study shows that supercell lattice dynamics calculations can accurately map the effect of orientational disorder on the phonon spectrum, paving the way for studying the vibrational entropy, thermal conductivity, and other thermodynamic effects in more complex materials.

Field-tuned quantum effects in a triangular-lattice Ising magnet.

We report thermodynamic and neutron scattering measurements of the triangular-lattice quantum Ising magnet TmMgGaO4 in longitudinal magnetic fields. Our experiments reveal a quasi-plateau state induced by quantum fluctuations. This state exhibits an unconventional non-monotonic field and temperature dependence of the magnetic order and excitation gap. In the high field regime where the quantum fluctuations are largely suppressed, we observed a disordered state with coherent magnon-like excitations despite the suppression of the spin excitation intensity. Through detailed semi-classical calculations, we are able to understand these behaviors quantitatively from the subtle competition between quantum fluctuations and frustrated Ising interactions.

Neutron Scattering Studies of the Breathing Pyrochlore Antiferromagnet LiGaCr_{4}O_{8}.

We report neutron scattering measurements of the spinel oxide LiGaCr_{4}O_{8}, in which magnetic ions Cr^{3+} form a breathing pyrochlore lattice. Our experiments reveal the coexistence of a nearly dispersionless resonance mode and dispersive spin-wave excitations in the magnetically ordered state, which can be quantitatively described by a quantum spin model of hexagonal loops and linear spin-wave theory with the same set of exchange parameters, respectively. Comparison to other Cr spinel oxides reveals a linear relationship between the resonance energy and lattice constant across all these materials, which is in agreement with our hexagonal loop calculations. Our results suggest a unified picture for spin resonances in Cr spinel oxides.

Low thermal conductivity in a modular inorganic material with bonding anisotropy and mismatch.

The thermal conductivity of crystalline materials cannot be arbitrarily low, as the intrinsic limit depends on the phonon dispersion. We used complementary strategies to suppress the contribution of the longitudinal and transverse phonons to heat transport in layered materials that contain different types of intrinsic chemical interfaces. BiOCl and Bi2O2Se encapsulate these design principles for longitudinal and transverse modes, respectively, and the bulk superlattice material Bi4O4SeCl2 combines these effects by ordering both interface types within its unit cell to reach an extremely low thermal conductivity of 0.1 watts per kelvin per meter at room temperature along its stacking direction. This value comes within a factor of four of the thermal conductivity of air. We demonstrated that chemical control of the spatial arrangement of distinct interfaces can synergically modify vibrational modes to minimize thermal conductivity.

The effect of particle size, morphology and support on the formation of palladium hydride in commercial catalysts.

The relative amounts of hydrogen retained by a range of supported palladium catalysts have been investigated by a combination of electron microscopy and spectroscopic techniques, including incoherent inelastic neutron scattering. Contrary to expectation, the hydrogen capacity is not determined solely by the metal particle size, but it is a complex interaction between the particle size and its state of aggregation. The nature of the support is not only integral to the amount of hydrogen held by the catalyst, it also causes a marked difference in the rate of release of stored hydrogen from palladium. It is more difficult to fully dehydrogenate palladium on/in the porous activated carbon than on the non-porous carbon black based catalyst. The type of support also results in differences in the form of the residual hydrogen: whether it is α- or ß-hydride phase, subsurface or in the threefold surface site. Our data on the supported catalysts reinforces what has only been seen previously with palladium black and our computational study provides confirmation of the empirical assignments. We also report the first vibrational spectroscopic study of hydrogen adsorbed at the surface of ß-PdH and have observed for the first time hydrogen in the on-top site. This has enabled the relative proportion of bulk- to surface-H occupation in calculated model and in industrial nanoparticles to be estimated.

Coulomb spin liquid in anion-disordered pyrochlore Tb2Hf2O7.

The charge ordered structure of ions and vacancies characterizing rare-earth pyrochlore oxides serves as a model for the study of geometrically frustrated magnetism. The organization of magnetic ions into networks of corner-sharing tetrahedra gives rise to highly correlated magnetic phases with strong fluctuations, including spin liquids and spin ices. It is an open question how these ground states governed by local rules are affected by disorder. Here we demonstrate in the pyrochlore Tb2Hf2O7, that the vicinity of the disordering transition towards a defective fluorite structure translates into a tunable density of anion Frenkel disorder while cations remain ordered. Quenched random crystal fields and disordered exchange interactions can therefore be introduced into otherwise perfect pyrochlore lattices of magnetic ions. We show that disorder can play a crucial role in preventing long-range magnetic order at low temperatures, and instead induces a strongly fluctuating Coulomb spin liquid with defect-induced frozen magnetic degrees of freedom.Experimental studies of frustrated spin systems such as pyrochlore magnetic oxides test our understanding of quantum many-body physics. Here the authors show experimentally that Tb2Hf2O7 may be a model material for investigating how structural disorder can stabilize a quantum spin liquid phase.

Hedonic and sensory characteristics of odors conditioned by pairing with tastants in humans.

Animals readily acquire positive odor-taste hedonic associations, but evidence for this in humans remains weak and was explored further. Retronasal pairing of odors with sucrose or salty stimuli (Experiment 1) increased the rated sweetness of sucrose-paired odors without altering liking, although changes in odor pleasantness correlated with sucrose liking. Experience of odors with sucrose or quinine by sweet likers (Experiment 2) found increased pleasantness and sweetness for sucrose-paired odors, whereas quinine-paired odors became less liked and more bitter. Odor-sucrose pairings in sweet likers and dislikers (Experiment 3) found increased sweetness in both groups but increased odor liking only in likers. These data suggest that evaluative and sensory learning are dissociable and that evaluative changes are sensitive to individual differences in sweet liking.