Methane hydrate has a unique structure that the host water framework forms two kinds of cages, which contain one methane molecule each. Therefore, it has been expected that there may exist three kinds of translational modes of a methane molecule and also the distortion of translational mode of host water molecules compared with normal ice. We need information of the host and guest molecular dynamics over the wide momentum and energy transfer region for studying such dynamics. In this study inelastic neutron measurements were carried under 40 K with MARI spectrometer at ISIS in UK, TAS at JRR-3 and CAT at KENS in Japan. For the methane molecular motion we could confirm its freelike rotation by complementary use of MARI and TAS spectra. After the subtraction of the scattering intensity of the rotation evaluated by the free rotation model from the experimental data, three kinds of translation modes were identified at first experimentally. On the experimental spectra there still remains the excess intensity which could not explain the single mode excitation. The libration mode of the water framework shows the different momentum and energy transfer dependence with those of normal ice. The feature of the libration mode is resemble to ice-IX, that could be considered as a proton ordering of the cage structure appeared in ice-II, VIII and IX.

Ferroelectric and ferromagnetic materials have been extensively studied for potential applications in sensors, actuators and transducers. Highly electrostrictive (1-x)Pb(Mg_1/3Nb_2/3)-xPbTiO₃ (PMN-xPT) and highly magnetostrictive Fe-xat.%Ga are two such novel materials. Both materials systems have chemical disorders and structural inhomogeneity on a microscale, giving rise to an interesting diversity of crystal structures and novel macroscopic physical properties, which are dependent on thermal and electrical histories of the crystals. In this thesis, I have to investigated phase transformations in these two systems under thermal and field (electric/magnetic) histories, using x-ray and neutron scattering techniques. In PMN-xPT crystals, x-ray and neutron diffractions were performed along the different crystallographic orientations and for different thermal and electrical histories. Various intermediate monoclinic (M) phases that structurally “bridge” the rhombohedral (R) and tetragonal (T) ones across a morphtropic phase boundary (MPB) have been observed. Systematic investigations of (001) and (110) electric (E) field-temperature phase diagrams of PMN-xPT crystals have demonstrated that the phase stability of PMN-xPT crystals is quite fragile: depending not only on modest changes in E (≤ 0.5kV/cm), but also on the direction along which E is applied. Structurally bridging monoclinic Mc or orthorhombic (O) phases were found to be associated with the T phase, whereas the monoclinic Ma or Mb phases bridged the Cubic (C) and R ones. In addition, neutron inelastic scattering was performed on PMN-0.32PT to study the dynamic origin of the MPB. Data were obtained between 100 and 600 K under various E applied along the cubic [001] direction. The lowest frequency zone-center, transverse optic phonon was strongly damped and softened over a wide temperature range, but started to recover on cooling into the T phase at the Curie temperature (TC). Comparisons of my findings with prior ones for PMN and PMN-0.60PT suggest that the temperature dependence and energy scales of the soft mode dynamics in PMN-xPT are independent of PT concentration below the MPB, and that the MPB may be defined in composition space x when TC matches the temperature at which the soft mode frequency begins to recover. High-resolution x-ray studies then showed that the C–T phase boundary shifted to higher temperatures under E by an expected amount within the MPB region: suggesting an unusual instability within the apparently cubic phase at the MPB. In Fe-xat.%Ga alloys, the addition of Ga atoms into the b.c.c. α-Fe phase also results in diversity of crystal structures and structural inhomogeneity, which are likely the source of its unusual magneto-elastic properties. I have carefully investigated decomposition of Fe-xat.%Ga alloys subjected to different thermal treatments by x-ray and neutron diffraction for 12 < x < 25. Quenching was found to suppress the formation of a DO₃ structure in favor of a high-temperature disordered bcc (A2) one. By contrast, annealing produced a two-phase mixture of A2 + DO₃ for 14 < x < 20 and a fully DO₃ phase for x = 25. A splitting of the (2 0 0) and (0 0 2) Bragg peaks observed along the respective transverse directions indicated that Fe-xat.%Ga –crystals' are composed of several crystal grain orientations (or texture structures), which are slightly tilted with respect to each other. In order to investigate the local structural distortions and heterogeneities, neutron diffuse scattering was performed on Fe-x%Ga alloys for different thermal conditions. Diffuse scattering around a (100) superlattice reflection was found for 14 < x < 22 in the furnace-cooled condition, indicative of short-range ordered DO₃ nanoprecipitates in an A2 matrix. This diffuse intensity had an asymmetric radial contour and an off-centering. Analysis (x=19) revealed two broad peaks with c/a–1.2: indicating that the DO₃-like nanoprecipitates are not cubic, but rather of lower symmetry with a large elastic strain. The strongest diffuse scattering was observed for x=19, which correspondingly had maximum magnetostriction: indicating a structural origin for enhanced magnetostriction. / Ph. D.

Growing environmental concerns, coupled with increasing regulatory restrictions, are requiring industries to develop non-lead-based compositions of ferroelectric and piezoelectric materials. These materials—now widely used in sensors, actuators, and transducers—are for the most part lead-based compounds such as Pb(Zr,Ti)O₃ (PZT). Indeed, PZT represents the dominant market share for use in these technologies. Moreover, next generation compounds, which include Pb(Mg_1/3Nb_2/3)O₃-xat%PbTiO₃ (PMN-x%PT) crystals with ultrahigh piezo-/electromechanical properties, are also Pb-based systems and thus are problematic for meeting more restrictive environmental standards. As alternative, Pb-free ferroelectrics such as NBT-derived single crystals represent viable next-generation materials for use in ferro-/piezoelectric applications. Development of these types of NBT-based crystals has made important advancements in the last decade. In fact, the performances of NBT-based materials are beginning to approach the properties of the widely used commercial PZT ceramic material. Nonetheless, additional studies are needed before it being able to compete with PMN-x%PT and PZN-x%PT crystals in next-generation applications. As a new type of piezoelectric material, much remains to be learned about Pb-free piezoelectric crystals. For instance, in addition to enhancing our understanding the nature of the piezoelectric third-rank tensor coefficients such as d₃₃ and d₁₅, a thorough knowledge of the Curie temperature, leakage current, and electromechanical properties is also essential for increasing the applications potential of these crystals. As detailed herein, multiple dopants may have to be incorporated into NBT to modify its microstructure and properties to meet these specific requirements, which may further complicate its chemical structure-property relationships. This study, therefore, was designed to investigate the heterogeneous structure of NBT-based single crystals, using x-ray diffraction, transmission electron microscopy, and neutron inelastic scattering, with the goal of investigating the mechanism coupling of morphotropic phase boundary (MPB) and the maximum property responses in A-site disordered perovskite Pb-free piezoelectric systems. Using the framework of polar nanoregions and adaptive phase theory, I sought to determine how the nanostructure of these single crystals change with temperature and composition—and how these factors impact its properties. Diffuse scattering, domain morphology, and phonon dispersions were used to investigate both the static and dynamic properties of these heterogeneous structures. / Ph. D.

Since the synthesis of Mn12, which can be regarded as the birth of the class of magnetic molecules, many different molecules of various sizes and structures have been produced. The magnetic nature of these molecules originates from a number of paramagnetic ions, whose unpaired electrons form collective angular momenta, referred to as spins. The interaction between these spins can often be described in the Heisenberg model. In this work, we use the rotational band model to predict the energy spectrum of the giant Keplerate {Mo72Fe30}. Based on the approximate energy spectrum, we simulate the cross-section for inelastic neutron scattering, and the results are compared to experimental data. The successful application of our approach substantiates the validity of the rotational band model. Furthermore, magnetic molecules can serve as an example for studying general questions of quantum mechanics. Since chemistry now allows the preparation of magnetic molecules with various spin quantum numbers, this class of materials can be utilized for studying the relations between classical and quantum regime. Due to the correspondence principle, a quantum spin system can be described exactly by classical physics for an infinitely large spin quantum number s. However, the question remains for which quantum numbers s a classical calculation yields a reasonable approximation. Our approach in this work is to develop a converging scheme that adds systematic quantum corrections to the classical density of states for Heisenberg spin systems. To this end, we establish a correspondence of the classical density of states and the quantum spectrum by means of spin-coherent states. The algorithm presented here allows the analysis of how the classical limit is approached, which gives general criteria for the similarity of the classical density of states to the quantum spectrum.