Quasielastic Neutron Scattering Study on Thermal Gelation in Aqueous Solution of Agarose.

The dynamics of water and agarose molecules in an agarose aqueous solution has been studied by means of quasielastic neutron scattering (QENS). The dynamic structure factor S (Q,E) of the agarose aqueous solution was fitted well to the sum of the Lorentz and delta function. The former is attributed to the diffusive motion of water molecules and the latter to the local vibrational motion of agarose molecules. The self-diffusion coefficient D of water molecules was obtained from the Q-dependence of the width of the Lorentz function, while the mean square displacement of agarose molecules was obtained from the Q-dependence of the intensity of the delta term. In the cooling direction, both D and decreased with decreasing temperature and showed discontinuous changes around the thermal gelation temperature (around 314 K). In the heating direction, however, D and did not show the obvious change below 343 K, indicating a large hysteresis effect. The present results of and D revealed that the thermal gelation suppresses the motion of the polymer and accelerates the diffusion of water molecules. The activation energy Ea of the diffusion of water in the sol state is the same as that of bulk water, but the Ea in the gel state is clearly smaller than that of bulk water.

Time-Resolved Structural Analysis of Fast-Photoresponsive Surfactant Micelles by Stroboscopic Small-Angle Neutron Scattering.

Photoresponsive materials are garnering attention because of their applications toward building a sustainable society. A recently developed fast-photoresponsive amphiphilic lophine dimer (3TEG-LPD) responds rapidly to light, making it a promising candidate for drug-delivery systems. In this study, the mechanism of structural changes induced by ultraviolet (UV) irradiation in 3TEG-LPD micelles in an aqueous solution was investigated via an in situ time-resolved small-angle neutron scattering (SANS) technique. Since subsecond resolution was necessary to observe the structural changes in the 3TEG-LPD micelles, stroboscopic SANS analysis was employed to obtain scattering profiles with a time width of 0.5 s. The structural parameters were quantitatively determined by performing a model-fitting analysis of the SANS results. The stroboscopic SANS results showed that upon UV irradiation, the axial ratio and pseudo-aggregation number of the 3TEG-LPD micelles increased by 1.8 and 1.6 times, respectively, whereas the number of water molecules per surfactant molecule decreased. This finding suggested that the change in the shape of the micelles from spherical to ellipsoidal shape was accompanied by dehydration. Under the present UV irradiation conditions, this structural change of the micelle occurred rapidly during the first 30 s after the start of UV irradiation. Each structural parameter recovered exponentially and reversibly during the recovery process after the cessation of UV irradiation. The changes in these parameters were analyzed in terms of kinetics by comparing them with the changes in the molecular structure. We found that the change of the micelles proceeds approximately twice as fast as the association of the molecule. Furthermore, from the perspective of the critical packing parameter consideration, the SANS analysis revealed that the UV-induced changes in 3TEG-LPD micelles are dominated by the enthalpy contribution. This finding is expected to be useful for developing new materials for various applications.

Polarized Neutrons Observed Nanometer-Thick Crystalline Ice Plates in Frozen Glucose Solution.

Spin-contrast-variation (SCV) small-angle neutron scattering (SANS) is a technique to determine the nanostructure of composite materials from the scattering of polarized neutrons that changes with proton polarization of samples. The SCV-SANS enabled us to determine structure of nanoice crystals that were generated in rapidly frozen sugar solutions by separating the overlapped signals from the nanoice crystals and frozen amorphous solutions. In the frozen glucose solution, we found that the nanoice crystals formed a planar structure with a radius larger than several tens of nanometers and a thickness of 2.5 ± 0.5 nm, which was close to the critical nucleation size of ice crystals in supercooled water. This result suggests that the glucose molecules were preferentially bound to a specific face of nanoice crystals and then blocked the crystal growth perpendicular to that face.

Magnon mode transition in real space.

Spin excitation of an ilmenite FeTiO3 powder sample is measured by time-of-flight inelastic neutron scattering. The dynamic magnetic pair-density function DM(r, E) is obtained from the dynamic magnetic structure factor SM(Q, E) by the Fourier transformation. The real space spin dynamics exhibit magnon mode transitions in the spin-spin correlation with increasing energy from no-phase-shift to π-phase-shift. The mode transition is well reproduced by a simulation using the reciprocal space magnon dispersions. This analysis provides a novel opportunity to study the local spin dynamics of various magnetic systems.

Optimization and inference of bin widths for histogramming inelastic neutron scattering spectra.

A data-driven bin-width optimization for the histograms of measured data sets based on inhomogeneous Poisson processes was developed in a neurophysiology study [Shimazaki & Shinomoto (2007). Neural Comput. 19, 1503-1527], and a subsequent study [Muto, Sakamoto, Matsuura, Arima & Okada (2019). J. Phys. Soc. Jpn, 88, 044002] proposed its application to inelastic neutron scattering (INS) data. In the present study, the results of the method on experimental INS time-of-flight data collected under different measurement conditions from a copper single crystal are validated. The extrapolation of the statistics on a given data set to other data sets with different total counts precisely infers the optimal bin widths on the latter. The histograms with the optimized bin widths statistically verify two fine-spectral-feature examples in the energy and momentum transfer cross sections: (i) the existence of phonon band gaps; and (ii) the number of plural phonon branches located close to each other. This indicates that the applied method helps in the efficient and rigorous observation of spectral structures important in physics and materials science like novel forms of magnetic excitation and phonon states correlated to thermal conductivities.

Quantum magnetisms in uniform triangular lattices Li2AMo3O8 (A = In, Sc).

Molecular based spin-1/2 triangular lattice systems such as LiZn2Mo3O8 have attracted research interest. Distortions, defects, and intersite disorder are suppressed in such molecular-based magnets, and intrinsic geometrical frustration gives rise to unconventional and unexpected ground states. Li2AMo3O8 (A = In or Sc) is such a compound where spin-1/2 Mo3O13 clusters in place of Mo ions form the uniform triangular lattice. Their ground states are different according to the A site. Li2InMo3O8 undergoes conventional 120° long-range magnetic order below TN = 12 K whereas isomorphic Li2ScMo3O8 exhibits no long-range magnetic order down to 0.5 K. Here, we report exotic magnetisms in Li2InMo3O8 and Li2ScMo3O8 investigated by muon spin rotation (µSR) and inelastic neutron scattering (INS) spectroscopies using polycrystalline samples. Li2InMo3O8 and Li2ScMo3O8 show completely different behaviors observed in both µSR and INS measurements, representing their different ground states. Li2InMo3O8 exhibits spin wave excitation which is quantitatively described by the nearest neighbor anisotropic Heisenberg model based on the 120° spin structure. In contrast, Li2ScMo3O8 undergoes short-range magnetic order below 4 K with quantum-spin-liquid-like magnetic fluctuations down to the base temperature. Origin of the different ground states is discussed in terms of anisotropies of crystal structures and magnetic interactions.

Multiple-wavelength neutron holography with pulsed neutrons.

Local structures around impurities in solids provide important information for understanding the mechanisms of material functions, because most of them are controlled by dopants. For this purpose, the x-ray absorption fine structure method, which provides radial distribution functions around specific elements, is most widely used. However, a similar method using neutron techniques has not yet been developed. If one can establish a method of local structural analysis with neutrons, then a new frontier of materials science can be explored owing to the specific nature of neutron scattering-that is, its high sensitivity to light elements and magnetic moments. Multiple-wavelength neutron holography using the time-of-flight technique with pulsed neutrons has great potential to realize this. We demonstrated multiple-wavelength neutron holography using a Eu-doped CaF2 single crystal and obtained a clear three-dimensional atomic image around trivalent Eu substituted for divalent Ca, revealing an interesting feature of the local structure that allows it to maintain charge neutrality. The new holography technique is expected to provide new information on local structures using the neutron technique.

Quasielastic neutron scattering studies on glass-forming ionic liquids with imidazolium cations.

Relaxation processes for imidazolium-based ionic liquids (ILs) were investigated by means of an incoherent quasielastic neutron scattering technique. In order to clarify the cation and anion effects on the relaxation processes, ten samples were measured. For all of the samples, we found three relaxations at around 1 ps, 10 ps, and 100 ps-10 ns, each corresponding to the alkyl reorientation, the relaxation related to the imidazolium ring, and the ionic diffusion. The activation energy (Ea) for the alkyl relaxation is insensitive to both anion and alkyl chain lengths. On the other hand, for the imidazolium relaxation and the ionic diffusion processes, Ea increases as the anion size decreases but is almost independent of the alkyl chain length. This indicates that the ionic diffusion and imidazolium relaxation are governed by the Coulombic interaction between the core parts of the cations (imidazolium ring) and the anions. This is consistent with the fact that the imidazolium-based ILs have nanometer scale structures consisting of ionic and neutral (alkyl chain) domains. It is also found that there is a clear correlation between the ionic diffusion and viscosity, indicating that the ionic diffusion is mainly associated with the glass transition which is one of the characteristics of imidazolium-based ILs.

Mode-distribution analysis of quasielastic neutron scattering and application to liquid water.

A quasielastic neutron scattering (QENS) experiment is a particular technique that endeavors to define a relationship between time and space for the diffusion dynamics of atoms and molecules. However, in most cases, analyses of QENS data are model dependent, which may distort attempts to elucidate the actual diffusion dynamics. We have developed a method for processing QENS data without a specific model, wherein all modes can be described as combinations of the relaxations based on the exponential law. By this method, we can obtain a distribution function B(Q,Γ), which we call the mode-distribution function (MDF), to represent the number of relaxation modes and distributions of the relaxation times in the modes. The deduction of MDF is based on the maximum entropy method and is very versatile in QENS data analysis. To verify this method, reproducibility was checked against several analytical models, such as that with a mode of distributed relaxation time, that with two modes closely located, and that represented by the Kohlrausch-Williams-Watts function. We report the first application to experimental data of liquid water. In addition to the two known modes, the existence of a relaxation mode of water molecules with an intermediate time scale has been discovered. We propose that the fast mode might be assigned to an intermolecular motion and the intermediate motion might be assigned to a rotational motion of the water molecules instead of to the fast mode.

Pressure dependence of local structure in liquid carbon disulfide.

High pressure x-ray diffraction measurements on liquid carbon disulfide up to 1.2 GPa are performed by using an energy dispersion method. The results are compared with a molecular dynamics calculation with usual Lennard-Jones potential. They give very good agreement for all pressures measured. It becomes clear that the liquid structure changes like hard core liquid up to the pressure just below crystallizing point. The relation between structural change and optical response at high pressure is discussed.

Macroscopic separation of dense fluid phase and liquid phase of phosphorus.

Structural transformation between a dense molecular fluid and a polymeric liquid of phosphorus that occurred at about 1 gigapascal and 1000 degrees C was investigated by in situ x-ray radiography. When the low-pressure fluid was compressed, dark and round objects appeared in the radiograph. X-ray diffraction measurements confirmed that these objects were the highpressure liquid. The drops grew and eventually filled the sample space. Decompressing caused the reverse process. The macroscopic phase separation supported the existence of a first-order phase transition between two stable disordered phases besides the liquid-gas transition. X-ray absorption measurements revealed that the change in density at the transition corresponds to about 40% of the density of the high-pressure liquid.