Dynamics of molecular associates in methanol/water mixtures.

The dynamics of molecular associates in a methanol/water mixture was investigated using quasielastic neutron scattering. By measuring the signal from four methanol/water samples differing only by their isotopic composition, the relative motion of the water to methanol molecules, i.e. their mutual dynamics, was determined at the nanoscale. The thus obtained nanoscopic mutual diffusion coefficient signals a significantly slower process than the single particle diffusion of either methanol or water in the system as well as their macroscopic mutual diffusion. The data do not provide any indication of microsegregation in this preeminent alcohol/water mixture; however, they do indicate the existence of long lived but dynamic molecular associates of water and methanol molecules. Analysis of the structural relaxation shows that the lifetime of molecular association through hydrogen bonding determines the fact that viscosity of the mixtures at intermediate concentrations is higher than that of both pure components.

Magnetic order and fluctuations in the quasi-two-dimensional planar magnet Sr(Co1-xNix)2As2.

We use neutron scattering to investigate spin excitations in Sr(Co1-xNix)2As2, which has a c-axis incommensurate helical structure of the two-dimensional (2D) in-plane ferromagnetic (FM) ordered layers for 0.013⩽x⩽0.25. By comparing the wave vector and energy dependent spin excitations in helical ordered Sr(Co0.9Ni0.1)2As2 and paramagnetic SrCO2As2, we find that Ni doping, while increasing lattice disorder in Sr(Co1-xNix)2As2, enhances quasi-2D FM spin fluctuations. However, our band structure calculations within the combined density functional theory and dynamic mean field theory (DFT+DMFT) failed to generate a correct incommensurate wave vector for the observed helical order from nested Fermi surfaces. Since transport measurements reveal increased in-plane and c-axis electrical resistivity with increasing Ni doping and associated lattice disorder, we conclude that the helical magnetic order in Sr(Co1-xNix)2As2 may arise from a quantum order-by-disorder mechanism through the itinerant electron mediated Ruderman-Kittel-Kasuya-Yosida (RKKY) interactions.

Anomalous helimagnetic domain shrinkage due to the weakening of the Dzyaloshinskii-Moriya interaction in CrAs.

CrAs is a well-known helimagnet with the double-helix structure originating from the competition between the Dzyaloshinskii-Moriya interaction (DMI) and antiferromagnetic exchange interaction J. By resonant soft-x-ray scattering, we observe the magnetic peak (0 0 qm) that emerges at the helical transition with TS ≈ 267.5 K. Intriguingly, the helimagnetic domains significantly shrink on cooling below ~255 K, opposite to the conventional thermal effect. The weakening of DMI on cooling is found to play a critical role here. It causes the helical wave vector to vary, ordered spins to rotate, and extra helimagnetic domain boundaries to form at local defects, thus leading to the anomalous shrinkage of helimagnetic domains. Our results indicate that the size of magnetic helical domains can be controlled by tuning DMI in certain helimagnets.

Spin Waves in Detwinned BaFe_{2}As_{2}.

Understanding magnetic interactions in the parent compounds of high-temperature superconductors forms the basis for determining their role for the mechanism of superconductivity. For parent compounds of iron pnictide superconductors such as AFe_{2}As_{2} (A=Ba, Ca, Sr), although spin excitations have been mapped out throughout the entire Brillouin zone, the respective measurements were carried out on twinned samples and did not allow for a conclusive determination of the spin dynamics. Here we use inelastic neutron scattering to completely map out spin excitations of ∼100% detwinned BaFe_{2}As_{2}. By comparing observed spectra with theoretical calculations, we conclude that the spin excitations can be well described by an itinerant model when taking into account moderate electronic correlation effects.

Quantum Magnetic Properties in Perovskite with Anderson Localized Artificial Spin-1/2.

Quantum magnetic properties in a geometrically frustrated lattice of spin-1/2 magnet, such as quantum spin liquid or solid and the associated spin fractionalization, are considered key in developing a new phase of matter. The feasibility of observing the quantum magnetic properties, usually found in geometrically frustrated lattice of spin-1/2 magnet, in a perovskite material with controlled disorder is demonstrated. It is found that the controlled chemical disorder, due to the chemical substitution of Ru ions by Co-ions, in a simple perovskite CaRuO3 creates a random prototype configuration of artificial spin-1/2 that forms dimer pairs between the nearest and further away ions. The localization of the Co impurity in the Ru matrix is analyzed using the Anderson localization formulation. The dimers of artificial spin-1/2, due to the localization of Co impurities, exhibit singlet-to-triplet excitation at low temperature without any ordered spin correlation. The localized gapped excitation evolves into a gapless quasi-continuum as dimer pairs break and create freely fluctuating fractionalized spins at high temperature. Together, these properties hint at a new quantum magnetic state with strong resemblance to the resonance valence bond system.

Thermal evolution of quasi-one-dimensional spin correlations within the anisotropic triangular lattice of α - NaMnO 2 .

Magnetic order on the spatially anisotropic triangular lattice of α - NaMnO 2 is studied via neutron diffraction measurements. The transition into a commensurate, collinear antiferromagnetic ground state with k = ( 0.5 , 0.5 , 0 ) was found to occur below T N = 22 K . Above this temperature, the transition is preceded by the formation of a coexisting, short-range ordered, incommensurate state below T IC = 45 K whose two-dimensional propagation vector evolves toward k = ( 0.5 , 0.5 ) as the temperature approaches T N . At high temperatures ( T > T IC ) , quasielastic scattering reveals one-dimensional spin correlations along the nearest-neighbor Mn-Mn "chain direction" of the MnO6 planes. Our data are consistent with the predictions of a mean-field model of Ising-like spins on an anisotropic triangular lattice, as well as the predominantly one-dimensional Heisenberg spin Hamiltonian reported for this material.

Origin of long lifetime of band-edge charge carriers in organic-inorganic lead iodide perovskites.

Long carrier lifetime is what makes hybrid organic-inorganic perovskites high-performance photovoltaic materials. Several microscopic mechanisms behind the unusually long carrier lifetime have been proposed, such as formation of large polarons, Rashba effect, ferroelectric domains, and photon recycling. Here, we show that the screening of band-edge charge carriers by rotation of organic cation molecules can be a major contribution to the prolonged carrier lifetime. Our results reveal that the band-edge carrier lifetime increases when the system enters from a phase with lower rotational entropy to another phase with higher entropy. These results imply that the recombination of the photoexcited electrons and holes is suppressed by the screening, leading to the formation of polarons and thereby extending the lifetime. Thus, searching for organic-inorganic perovskites with high rotational entropy over a wide range of temperature may be a key to achieve superior solar cell performance.

Entropy-driven structural transition and kinetic trapping in formamidinium lead iodide perovskite.

A challenge of hybrid perovskite solar cells is device instability, which calls for an understanding of the perovskite structural stability and phase transitions. Using neutron diffraction and first-principles calculations on formamidinium lead iodide (FAPbI3), we show that the entropy contribution to the Gibbs free energy caused by isotropic rotations of the FA+ cation plays a crucial role in the cubic-to-hexagonal structural phase transition. Furthermore, we observe that the cubic-to-hexagonal phase transition exhibits a large thermal hysteresis. Our first-principles calculations confirm the existence of a potential barrier between the cubic and hexagonal structures, which provides an explanation for the observed thermal hysteresis. By exploiting the potential barrier, we demonstrate kinetic trapping of the cubic phase, desirable for solar cells, even at 8.2 K by thermal quenching.

Liquid-Liquid Phase Transition and Its Phase Diagram in Deeply-Cooled Heavy Water Confined in a Nanoporous Silica Matrix.

Using neutron diffraction technique, we measure the average density of the heavy water confined in a nanoporous silica matrix, MCM-41, over the pressure-temperature plane. The result suggests the existence of a line of liquid-liquid phase transition with its end point at 1.29 ± 0.34 kbar and 213 ± 3 K in a fully hydrated sample. This point would be the liquid-liquid critical point (LLCP) according to the "liquid-liquid critical point" scenario. The phase diagram of the deeply cooled confined heavy water is then discussed. Moreover, in a partially hydrated sample, the phase transition completely disappears. This result shows that it is the free water part, rather than the bound water part, of the confined water that undergoes a liquid-liquid transition.

Evidence of the existence of the high-density and low-density phases in deeply-cooled confined heavy water under high pressures.

The average density of D2O confined in a nanoporous silica matrix (MCM-41-S) is studied with neutron scattering. We find that below ~210 K, the pressure-temperature plane of the system can be divided into two regions. The average density of the confined D2O in the higher-pressure region is about 16% larger than that in the lower-pressure region. These two regions could represent the so-called "low-density liquid" and "high-density liquid" phases. The dividing line of these two regions, which could represent the associated 1st order liquid-liquid transition line, is also determined.

Ferro-orbital ordering transition in iron telluride Fe(1+y)Te.

Fe(1+y)Te with y≲0.05 exhibits a first-order phase transition on cooling to a state with a lowered structural symmetry, bicollinear antiferromagnetic order, and metallic conductivity, dρ/dT>0. Here, we study samples with y=0.09(1), where the frustration effects of the interstitial Fe decouple different orders, leading to a sequence of transitions. While the lattice distortion is closely followed by incommensurate magnetic order, the development of bicollinear order and metallic electronic coherence is uniquely associated with a separate hysteretic first-order transition, at a markedly lower temperature, to a phase with dramatically enhanced bond-order wave (BOW) order. The BOW state suggests ferro-orbital ordering, where electronic delocalization in ferromagnetic zigzag chains decreases local spin and results in metallic transport.

Spin waves and magnetic exchange interactions in insulating Rb(0.89)Fe(1.58)Se(2).

The parent compounds of iron pnictide superconductors are bad metals with a collinear antiferromagnetic structure and Néel temperatures below 220 K. Although alkaline iron selenide A(y)Fe(1.6+x)Se(2) (A=K, Rb, Cs) superconductors are isostructural with iron pnictides, in the vicinity of the undoped limit they are insulators, forming a block antiferromagnetic order and having Néel temperatures of roughly 500 K. Here we show that the spin waves of the insulating antiferromagnet Rb(0.89)Fe(1.58)Se(2) can be accurately described by a local moment Heisenberg Hamiltonian. A fitting analysis of the spin wave spectra reveals that the next-nearest neighbour couplings in Rb(0.89)Fe(1.58)Se(2), (Ba,Ca,Sr)Fe(2)As(2), and Fe(1.05)Te are of similar magnitude. Our results suggest a common origin for the magnetism of all the Fe-based superconductors, despite having different ground states and antiferromagnetic orderings.

Transition from three-dimensional anisotropic spin excitations to two-dimensional spin excitations by electron doping the FeAs-based BaFe1.96Ni0.04As2 superconductor.

We use neutron scattering to study the effect of electron doping on the structural or magnetic order in BaFe2As2. In the undoped state, BaFe2As2 exhibits simultaneous structural and magnetic phase transitions below 143 K. Upon electron doping to form BaFe1.96Ni0.04As2, the system first displays the lattice distortion near approximately 97 K, and then orders antiferromagnetically at 91 K before developing weak superconductivity below approximately 15 K. The effect of electron doping is to reduce the c-axis exchange coupling in BaFe2As2 and induce quasi-two-dimensional (2D) spin excitations. These results suggest that the transition from 3D spin waves to quasi-2D spin excitations by electron doping is important for the separated structural and magnetic phase transitions in iron arsenides.

Inelastic neutron-scattering measurements of a three-dimensional spin resonance in the FeAs-based BaFe1.9Ni0.1As2 superconductor.

We use inelastic neutron scattering to study magnetic excitations of the FeAs-based superconductor BaFe1.9Ni0.1As2 above and below its T_{c} (=20 K). In addition to gradually open a spin gap at the in-plane antiferromagnetic ordering wave vector (1, 0, 0), the effect of superconductivity is to form a three-dimensional resonance with clear dispersion along the c axis. The intensity of the resonance develops like a superconducting order parameter, and the mode occurs at distinctively different energies at (1, 0, 0) and (1, 0, 1). If the resonance energy is associated with the superconducting gap energy Delta, then Delta is dependent on the wave vector transfers along the c axis. These results suggest that one must be careful in interpreting the superconducting gap energies obtained by surface sensitive probes such as scanning tunneling microscopy and angle resolved photoemission.