The langasites are a class of geometrically frustrated compounds with the formula A3XY3Z2O14 where A,X,Y,Z are cationic sites and site A is occupied by a magnetic ion. The interactions of the magnetic ions form a star shaped pattern called the Kagomé lattice. The langasites have been widely studied by the solid state community because of their functional properties such as piezoelectricity, multiferroicity, ferroelectricity, dielectricity and for use in the telecommunication industry. It was also realized that some langasite materials exhibit exotic magnetic ground states at low temperatures. A thorough understanding of their ground state is limited by the difficulty in synthesizing new members belonging to this series due to the formation of competing phases such as the garnets. In this study, four new magnetic langasites A3Ga3Ge2BeO14 (A= Pr, Nd, Sm and Eu) and a non-magnetic lattice standard La3Ga3Ge2BeO14 were synthesized. These were further structurally characterized by powder X-ray diffraction, Rietveld refinement and bond valence analysis. Further characterization of the low-temperature magnetism was done by performing magnetization, magnetic susceptibility (field cooled and zero field cooled) and heat capacity measurements. The low temperature spin dynamics were probed using muon spin resonance performed at TRIUMF (Vancouver) and elastic and inelastic neutron scattering measurements performed at the DCS (NIST) and D7 (ILL). From all the above measurements it can be concluded that the new Be langasites exhibit net antiferromagnetic interactions at low-temperatures with clear signs of diffuse scattering for Nd3Ga3Ge2BeO14 using inelastic neutron scattering measurements. There was no evidence of magnetic long-range ordering down to as low as 0.025 K. Based on the obtained measurements these new Be-langasite compounds can be classified as potential spin liquid candidates. / February 2017

This thesis describes inelastic neutron scattering (INS) experiments on several iron-based materials. The experiments were primarily designed to investigate the link between magnetic dynamics and superconductivity. The work contributes to evidence that magnetic fluctuations influence or are influenced by superconductivity. It is demonstrated that the INS response of a material, in conjunction with theoretical models, can provide valuable information about both superconductivity and magnetism. I measured the magnetically ordered parent-compound SrFe2As2 to investigate the nature of magnetism in iron-based systems. Comparison of the data to models based on both itinerant and localised magnetism showed that an itinerant model offers the best description of the data. LiFeAs is a superconductor that shows no magnetic order, however I was able to distinguish a magnetic signal in its INS spectrum. The signal is consistent with the magnetic resonance observed in several other iron-based superconductors. This indicates that LiFeAs likely hosts an s± gap symmetry. I investigated two iron-phosphide systems, LaFePO and Sr2ScO3FeP, and in this case I was unable to identify any magnetic scattering. Comparison to LiFeAs showed that any signal in LaFePO is at least 7 times weaker. These results suggest that magnetic fluctuations are not as influential to the electronic properties of iron-phosphide systems as they are in other iron-based superconductors. In CsxFe2−ySe2 I found two independent signals that appear to be related to phase-separated magnetic and superconducting regions of the sample. I showed that fluctuations associated with the magnetically ordered phase are consistent with localised magnetism, and do not respond to superconductivity. The second signal, however, increases in intensity below the superconducting transition temperature Tc = 27K, consistent with a magnetic resonance. This could be indicative of a pairing symmetry in CsxFe2−ySe2 that is distinct from most other iron-based superconductors. Finally, the molecular intercalated FeSe compound Li0.6(ND2)0.2(ND3)0.8Fe2Se2 revealed strong magnetic fluctuations. Again the signal was consistent with a magnetic resonance responding to Tc = 43 K. The results suggest that Lix(ND2)y(ND3)1−yFe2Se2 is similar to the superconducting phase of CsxFe2−ySe2, placing constraints on theoretical models to describe the molecular intercalated FeSe compounds.

Neutron scattering measurements were used to investigate the magnetic and crystal structure and magnetic excitations of three compounds characterized as low-dimensional quantum magnets. The materials are frustrated systems with low spin quantum number. The first was a powder sample of AgNiO₂. The Ni ions form a triangular lattice antiferromagnet in which, according to the published crystal structure, both the orbital order and magnetic couplings are frustrated. However, it is shown here that there was a small distortion of the crystal structure at 365 K, which is proposed to result from charge disproportionation and this relieves the orbital frustration. The magnetic structure was investigated and, below 20 K, the triangular lattice of electron-rich Ni sites was observed to order into antiferromagnetic stripes. Investigations of the magnetic excitations showed that the main dispersions were within the triangular plane, indicating a strong two-dimensionality. The dispersion was larger along the stripes than between the stripes of collinear spins. The second material investigated was CoNb₂O₆, a quasi Ising-like ferromagnet. It was studied with a magnetic field applied transverse to the Ising direction. The magnetic field introduced quantum fluctuations which drove a phase transition at a field comparable to the main exchange interaction. The phase diagram of the magnetic order was mapped outs and a transition from an ordered phase to a paramagnetic phase was identified at high field. This low-temperature high-field phase transition was further investigated by inelastic neutron scattering measurements to observe the change in the energy gap and magnetic excitation spectrum on either side of the transition. The spectrum had two components in the ordered phase and had sharp magnon modes in the paramagnetic phase. The third material was the spin-half layered antiferromagnet CuSb₂O₆. It has a square lattice of Cu²⁺ ions in which the main interaction is across only one diagonal of the square. The magnetic structure was studied by neutron scattering with a field applied along the direction of the zero-field ordered moment. A spin-flop was observed at low field and there was evidence for a high-field transition. The magnetic excitation spectrum was unusual in that it had an intense resonance at 13 meV at the magnetic Brillouin zone boundary.

This thesis presents three investigations of the magnetic and electronic proper- ties of manganese oxide materials. The investigations are performed using a variety of neutron scattering and x-ray scattering techniques. The electronic ground-state of Pr(Sr_0.1 Ca_0.9)₂ Mn₂O₇ an antiferromagnet with CE-type ordering, is determined using neutron spectroscopy, as opposed to the more usual approach of using diffraction. The Zener polaron model of the elec- tronic ground state of the CE-type magnetic phase is shown to be unsuitable for this material. The ground-state is shown to agree well with the electronic ground state proposed by Goodenough in the 1950’s, but without significant Mn^3+/Mn^4+ disproportionation. The distribution of the magnetisation density within the unit cell of the CE-type antiferromagnet La_0.5Sr_1.5MnO₄ is determined from a polarised neutron diffraction experiment by analysing the results with the maximum entropy method. The majority of the magnetisation density is found to be located at the Mn site. The investigation shows tentative evidence of a small magnetic moment on the in-plane O site. However, a larger moment is observed at both the La/Sr site and the out-of-plane O site. The magnetic structure of the magnetoelectric multiferroic DyMn₂O₅ is inves- tigated using resonant magnetic x-ray scattering. The magnetic structure is shown to be similar to other members of the RMn₂O₅ series of multiferroics, but with the key difference that the magnetic moments are closely aligned parallel with the crystallographic b-axis, in contrast to the usual observation of the moments being close to parallel with the a-axis. This study also shows evidence that the electrical polarisation has a significant contribution from the valence electrons of the O ions, agreeing with previous work.

La plupart des solides dans la vie quotidienne, tels que les métaux et les céramiques, sont des systèmes cristallins dans lesquels les atomes ou molécules sont arrangés sur une structure périodique. Les solides cristallins sont rarement composés d'un cristal unique, mais sont en général des systèmes polycristallins formés par un grand nombre de grains cristallins avec une même structure cristalline, mais différente orientation. On appelle joints de grain (JG) les réseaux 2D de défauts qui séparent deux grains d'orientation différente. Les polycristaux jouent un rôle important en science et technologie et une connaissance complète de leurs propriétés mécaniques est de grand intérêt. La plasticité des polycristaux est liée à leur microstructure, mais les mécanismes qui régissent leur comportement plastique sont encore mal compris, en partie du fait de limitations techniques pour les systèmes atomiques. D'autre part, les colloïdes, dont l'étude expérimentale est souvent plus aisée que celle des systèmes atomiques, du fait de temps et taille caractéristiques plus grands, sont souvent considérés comme des systèmes modèles pour les atomes. L'objectif de la thèse est l'étude des propriétés mécaniques d'un polycristal colloïdal formé par une suspension aqueuse d'un copolymère tribloc commercial (Pluronic F108), dopé par une faible quantité de nanoparticules (NPs). Le polymère présente une phase micellaire cristalline pour une gamme de température et de concentration. De manière similaire à ce qui est fait couramment pour les systèmes atomiques, on peut contrôler le taux de cristallisation en faisant varier la vitesse à laquelle l'échantillon est porté de la phase liquide à basse température (T ~ 0°C) à la phase micellaire cristalline à température ambiante. Une caractéristique importante est que la taille des grains peut être facilement contrôlée en faisant varier la vitesse d'augmentation de la température ou la concentration en NPs. Dans un premier temps, nous avons caractérisé la structure du polycristal par diffusion de neutrons (SANS) et de lumière. Les mesures par SANS ont permis de sonder la structure du polycristal à l'échelle du nanomètre, i.e. sur des échelles de longueur comparable à celle des micelles et des NPs. Nous avons constaté que la structure cristalline micellaire est conservée indépendamment de l'histoire thermique de l'échantillon et de la concentration en NPs. De plus, nous avons montré que la distribution des NPs dans l'échantillon est hétérogène: les grains sont pauvres en NPs alors que les JG sont enrichies en NPs. Par conséquent, les NPs ségrégent dans les JG et et jouent un rôle analogue aux impuretés dans les cristaux atomiques. En outre, en raison de leur ségrégation, les NPs sont structurées sur une échelle de longueur beaucoup plus grande que leur taille. Nous avons étudié la structure mésoscopique des NPs par diffusion statique de la lumière, grâce à un appareil de diffusion de la lumière (MALS) spécialement construit pour accéder à la plage correcte de vecteurs d'onde. D'autre part, afin d'étudier les propriétés mécaniques des polycristaux, des mesures de diffusion dynamique de la lumière ont été réalisée dans la configuration MALS sur un échantillon soumis à des déformations de cisaillement cycliques. Dans la configuration MALS, l'intensité diffusée étant dominée par les NPs dans les JG, la technique permet de sonder la dynamique du réseau de JG induite par le cisaillement. Expérimentalement, on calcule la corrélation de l'intensité diffusée mesurée après un nombre donné de cycles de déformation. Les données montrent systématiquement une décroissance de la corrélation après un nombre caractéristique de cycles, démontrant ainsi l'existence de plasticité dans les échantillons. À l'avenir, des échantillons avec des tailles de grain différentes seront étudiés. De telles expériences pourraient faire la lumière sur les liens entre plasticité d'un polycristal colloïdal et microstructure. / Most everyday life solids, such as metals and ceramics, are crystalline systems in which atoms or molecules are arranged in a regular periodic structure. Crystalline solids are rarely composed of one single crystal, but are usually polycrystalline systems made of a large number of crystalline regions (grains), which share a common crystal structure, but with different lattice orientations. The interfaces where crystallites meet are denoted as grain boundaries (GBs). Polycrystalline materials play an important role in science and technology and a complete knowledge of their mechanical properties, including their elasticity and plasticity, is of great interest. It is well known that the plasticity of polycrystals is related to their microstructure, but the mechanism governing the plastic behavior is still poorly understood, partly because of the limits of experimental techniques and simulations for atomic polycrystals. On the other hand, colloids are often regarded as model systems for atoms, since many of the forces governing the behavior of condensed matter govern also that of colloidal suspensions, whose experimental study is often easier than that of atomic systems because of the larger characteristic time- and length-scales. In particular, colloidal crystalline systems can be used to investigate mechanical properties of polycrystals. The aim of the PhD thesis is the investigation of the mechanical properties of a colloidal polycristal formed by an aqueous suspension of a commercial triblock copolymer called Pluronic F108, doped with a small amount of nanoparticles (NPs). The polymer presents a micellar crystalline phase for a given range of temperature and concentration. Similarly to what is commonly done for atomic systems, we can control the crystallization rate by varying the speed at which the sample is brought from the fluid, at low temperature (T ~ 0°C), to the crystal phase at room temperature. An important characteristic of our system is that the grain size can be easily tuned by changing the temperature rate or the nanoparticles concentration. We have first characterized the structure of the Pluronic polycrystal using neutron (SANS) and light scattering. The SANS measurements have permitted to investigate the (doped) Pluronic polycrystal at nanometer length scale, i.e. at the length scale of the micelles and nanoparticles. We have found that the micellar crystal structure is preserved independently of the thermal history of the sample and the amount of added nanoparticles. Moreover, we have shown that the NPs distribution into the sample is heterogeneous: grains are poor in NPs whereas GBs are enriched in NPs. Hence, NPs segregate into the GBs as impurities in atomic crystals. In addition, because of their segregation in the GBs, NPs form structures on a length scale much larger than their size, that we have investigated with static light scattering, thanks to a novel light scattering apparatus (MALS) specifically built to access the correct range of wave-vectors. On the other hand, in order to investigate the mechanical properties of the Pluronic crystal, dynamic light scattering measurements have been performed with the MALS setup on the Pluronic polycrystal submitted to cyclic shear deformations. Since, in the range of wave-vectors covered by the MALS apparatus, the scattered intensity is dominated by the NPs segregated in the GBs, the techniques allows the shear-induced dynamics of the GB network to be probed. Experimentally, one computes the correlation of the scattered intensity measured after a given number of shear deformation cycles. Data systematically show that the correlation decays after a characteristic number of cycles, demonstrating the existence of plasticity. In future, samples with different grain size will be investigated with this technique. Such experiments could shed light on how the plasticity of a colloidal polycrystal is related to its polycrystalline microstructure.

Thesis advisor: Stephen D. Wilson / Iridium-based members of the Ruddlesden-Popper family of oxide compounds are characterized by a unique combination of energetically comparable effects: crystal-field splitting, spin-orbit coupling, and electron-electron interactions are all present, and the combine to produce a Jeff = 1/2 ground state. In the bilayer member of this series, Sr3Ir2O7, this state manifests as electrically insulating, with unpaired Ir4+ spins aligned along the long axis of the unit cell to produce a G-type antiferromagnet with an ordered moment of 0.36 uB. In this work, this Mott state is destabilized by electron doping via La3+ substitution on the Sr-site to produce (Sr1−x Lax)3Ir2O7. The introduction of carriers initially causes nano-scale phase-separated regions to develop before driving a global insulator-to-metal transition at x=0.04. Coinciding with this transition is the disappearance of evidence of magnetic order in the system in either bulk magnetization or magnetic scattering experiments. The doping also enhances a structural order parameter observed in the parent compound at forbidden reciprocal lattice vectors. A more complete structural solution is proposed to account for this previously unresolved distortion, and also offers an explanation as to the anomalous net ferromagnetism seen prior in bulk measurements. Finally, spin dynamics are probed via a resonant x-ray technique to reveal evidence of spin-dimer-like behavior dominated by inter-plane interactions. This result supports a bond-operator treatment of the interaction Hamiltonian, and also explains the doping dependence of high temperature magnetic susceptibility. / Thesis (PhD) — Boston College, 2016. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Physics.

Thesis advisor: Stephen D. Wilson / Spin-orbit intertwined order gives rise to many novel phenomena with a broad phase space spanned by the competing energy scales within a system. This dissertation synthesized and studied two such systems demonstrating different manifestations of spin-orbit interactions, originating from orbital degeneracy effects, on geometrically frustrated magnetic lattices. Firstly, strong spin-orbit coupling in the hyperkagome lattice, Na4Ir3O8, and secondly, the layered material, α-NaMnO2, where single-ion anisotropy and a cooperative Jahn-Teller distortion drive magnetism to the quasi-1D limit. The magnetic ground state of the Jeff = 1/2 spin-liquid candidate, Na4Ir3O8, is explored via combined bulk magnetization, muon spin relaxation, and neutron scattering measurements. A short-range, frozen, state comprised of quasi-static moments develops below a characteristic temperature of TF = 6 K, revealing an inhomogeneous distribution of spins occupying the entirety of the sample volume. Quasi-static, short-range, spin correlations persist until at least 20 mK and differ substantially from the nominally dynamic response of a quantum spin liquid. Much of this dissertation focuses on the second spin-orbit intertwined system, α-NaMnO2, where a cooperative Jahn-Teller distortion of the MnO6 octahedra arising from an orbital degeneracy in the Mn3+ cations directly affects the electronic (ferro-orbital) and magnetic (antiferromagnetic) order, which results in an intriguing study of low-dimensional magnetism. Intricacies of the structure, static magnetic order, and magnon dynamics are presented, which heavily relied on neutron scattering techniques. In particular, a longitudinally polarized bound magnon mode is characterized through the use of polarized neutron scattering. / Thesis (PhD) — Boston College, 2018. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Physics.

Silicon (in the form of lithium silicides) has almost ten times the theoretical charge storage capacity of graphite, the anode material used in most commercially-available lithium-ion batteries. Replacing graphite with silicon therefore promises a substantial improvement over the state-of-the-art in electrochemical energy storage. However, it has proved difficult to realise this high theoretical capacity in a practical electrochemical cell and maintain it over repeated charge-discharge cycles. This dissertation presents experimental work probing the changes in local structure occurring during the electrochemical reactions of lithium with silicon, using neutron total scattering and nuclear magnetic resonance, together with novel processing methodologies for analysing the resulting data, in the hope of suggesting ways of improving the performance of silicon-based lithium-ion batteries. Neutron total scattering patterns were obtained from silicon-based anode materials extracted from cells at various states of charge. These samples were composed of a heterogeneous mixture of amorphous, crystalline and disordered crystalline materials. Reverse Monte Carlo is a technique for obtaining structural information from experimental data (particularly total scattering patterns) from amorphous and disordered crystalline materials. However, previously existing Reverse Monte Carlo software could only handle homogeneous materials. Therefore, the RMCprofile software package was extended to handle data from heterogeneous samples. The improved RMCprofile was applied to the aforementioned total scattering patterns, but the much stronger scattering from the other components (themselves not well-characterised) swamped that from the lithium silicide. Future work should attempt to reduce the scattering from the inactive components, particularly the hard-to-model incoherent scattering. NMR data were acquired in situ from silicon-nanowire-based lithium-ion batteries during repeated charge-discharge cycles, achieving much better electrochemical performance than had been seen in previous in situ experiments with silicon. Owing to the large quantities of data obtained, an automated, model-free dimensionality reduction technique was needed. The NMR data were processed using principal component analysis and a variant of non-negative matrix factorisation. With both of these methods, one of the components was found to be associated with high voltages vs. ${Li \vert{} Li^{+}}$ (i.e. a fully discharged anode). This region has seen very little interest by comparison with the low voltage (high levels of lithiation) region of the charge-discharge cycle, so this discovery suggests a new avenue for future research.

The evolution of drug resistant pathogens creates the need for the introduction of new antimicrobial drugs. Peptaibols, a class of naturally occurring peptides, contain large amounts of alpha aminoisobutyric acid (Aib). They are known to exhibit their antimicrobial activity by perturbing the membranes of pathogens. However, a comprehensive model of action for these peptides has not yet been identified. Aib residues support the formation of 310-helix conformation and it is thought that this secondary structure is important for their antimicrobial activity. It is possible to design small synthetic peptides, known as foldamers, endowed with specific properties; in particular, Aib-rich foldamers are used as a model for the understanding of the folding and membrane interaction of the naturally occurring species. The aim of this thesis is to investigate the conformational preference of monodisperse Aib-oligomers as well as understanding their interaction with bilayer membranes. A large set of spectroscopic techniques have been used to establish the conformation of Aib-rich foldamers both in solution and when bound to membranes. In particular: Raman, Raman Optical Activity (ROA), Infrared (IR), Vibrational Circular Dichroism (VCD), Linear Dichroism (LD) and Neutron Scattering (NR) were employed to provide new structural insights. These vibrational analysis (VA) and vibrational optical analysis (VOA) investigations in solution were focused on the identification of spectral features for 310-helix conformation, particularly with Raman and Raman Optical Activity spectroscopies. Spectroscopic markers for this conformation in the amide I region were successfully identified. Moreover, it is known that chiral Aib-rich peptides can show a right or left handed screw-preference based on the primary sequence. VOA studies successfully distinguished between peptides with opposite helicity. VCD, ROA, LD and NR of Aib-foldamers bound to membranes were shown to be useful for identification of conformational preferences of the peptides within the membrane as well as for determining their orientation in the bilayer, and ultimately the effect of the peptides on the membrane structure.

The hydrophobic effect has been a topic of research for decades, not only due to its importance as the primary building block of much of chemistry (it dictates which solvent can dissolve which solutes) and biology (guiding protein binding and gene expression) but also due to it being a fundamental physical process. The commonly held opinion is that 'like dissolve like', implying polar substances can readily mix with other polar substances, and similarly for apolar ones, but polar and apolar would separate and tend to stay isolated from one another (like oil in water). We have developed a quantitative imaging method that can be used in tandem with Raman spectroscopy in order to investigate the effect of high pressure on a model hydrophobic system - water and methane. Our study revealed an unexpectedly large increase in the amount of methane that can readily mix with water once a rather modest pressure has been applied to the system. Thus, the solubility of CH4 in H2O starts abruptly increasing at 1.3 GPa and reaches a maximum of 44(3) mole % at 2.1 GPa, showing no pressure dependence upon further compression. We have tried to reproduce the observed experimental behaviour using classical molecular dynamics simulations deploying a range of widely used water potentials (SPC/E, TIP4P, TIP3P), but unfortunately no quantitative or even qualitative agreement was reached with experiments. Finally, in order to understand the atomic level changes that enable this increased amount of methane to dissolve in water, we have performed neutron scattering measurements along with EPSR (empirical potential structure refinement) fits to the data in order to solve the structure of the fluid mixture. These revealed a tendency towards maintaining the H-bond network present in water and homogeneous mixing. Despite the network staying similar to the one found in pure fluid water at milder pressures and temperatures (close to ambient conditions), the H-bonds seem more disordered and show a greater variability in their lengths.