The mobility of N-alkyl nicotinamides and their solubilization equilibria in surfactant micellar solution were investigated using an NMR paramagnetic relaxation method. The spin-lattice relaxation times (Tl) . for protons of these compounds were measured in pure D20 and in cationic surfactant solution in the presence and absence of · a low concentration of paramagnetic Ma2+ ions. The rotational motion of these molecules in aqueous phase became slower when the alkyl group changed from methyl to octyl. The increase of the 1H spinlattice relaxation rate (Rl) of the molecules, when surfactants are added, implies the penetration of these solubilizates into micellar phase. The micelle to water phase distribution coefficient, 1-p, was determined by monitoring the change of Rl of the solubilizates upon addition of paramagnetic ions to the aqueous phase. The mole fraction based distribution coefficient, Kx, as well as the free energy of transfer of N-alkyl nicotinamides from the aqueous phase to the micellar phase were calculated. A model was postulated for the interaction of N -alkyl nicotinamide with micelles. Hydrophobic force between the alkyl chains of the solubilizates and the surfactants accounts for the solubilization of N -alkyl nicotinamides and can force the binding of cationic compounds to cationic micelles · despite charge repulsion. With increasing of the alkyl chain length, the hydrophobic force increases, and the interaction between them becomes stronger, and more N -alkyl nicotinamides are solubilizated into the micellar phase.

The exploration of physical extremes drives technological innovation. Recent decades have seen a push towards materials engineering at the absolute limit of space with electronic systems that are a single atom thick. When electrons are confined to two-dimensional structures, exotic and often unexpected phenomena emerge due to enhanced interaction effects and crystalline anisotropies. The study of such unconventional phenomena offers the opportunity to extend knowledge of fundamental physics with an eye towards advancing the state of the art in control over quantum matter. In this thesis we use scanning tunneling microscopy to study the electronic structure of a collection of novel two-dimensional materials: twisted double-bilayer graphene (TDBG), mirror symmetric twisted trilayer graphene (TTG), small angle twisted double trilayer graphene (TDTG), and the van der Waals heavy Fermion material CeSiI. In TDBG, we directly image spontaneous symmetry breaking of the electronic states as a function of carrier density and attribute this to an intrinsic nematic instability of the metallic Fermi liquid. In TTG, we find evidence for a novel form of lattice relaxation, in which twist angle disorder leads to the formation of moiré lattice defects that can act to lock trilayer devices into a magic angle configuration while strongly modulating the local electronic structure, with implications for the superconducting state. In TDTG, we discover yet another form of lattice relaxation in which a global transformation of the stacking structure creates a net energy reduction, even while the stacking energy density in roughly half of the moiré lattice rises. Lastly, we show through quasiparticle interference spectroscopy and theoretical modeling that CeSiI hosts a nodal hybridization between itinerant conduction electrons and a lattice of local moments, giving rise to a strong angular dependence of the heavy Fermion mass enhancement in this van der Waals material.

Spin-lattice (T1) relaxation studies using solid-state and solution-state :31p nuclear magnetic resonance spectroscopy have proven to be a reliable procedure for determining the onset of a "liquid-like" character of the supported phase in a supported aqueous phase catalyst. It has also been shown that the appearance of the liquid-like character, which can be determined by the length of T b occurs at the onset of maximum catalytic activity in a supported aqueous phase catalyst. Direct sulfonation of 1,2-bis(diphenylphosphino)ethane (DPPE) has yielded 1,2-(bis[di-m-sodiumsulfonato]phenylphosphino)ethane (DPPETS), a new water soluble ligand that has been characterized and used in the synthesis of several new complexes with palladium, rhodium, platinum and nickel centers. T 1 relaxation times and the magnitude of the chemical shift anisotropy of several of the complexes have been determined with solid- and solution-state 31 P NMR and several complexes have been evaluated for their potential in biphasic hydrogenation and hydroformylation catalysis. / Ph. D.

No description available.

A taxa de relaxação magnética nuclear de uma impureza diluída em um meio metálico foi calculada como função da temperatura. Nossos cálculos são aplicados ao modelo de Anderson com degenerescência de spin, originalmente desenvolvido para descrever ligas magnéticas diluídas. Nossos cálculos são aplicados ao modelo de Anderson com degenerescência de spin, originalmente desenvolvido para descrever ligas magnéticas diluídas. Discutimos a relevância a sistemas de férmions pesados, valência flutuante e adsorção química em superfícies metálicas. As taxas de relaxação como função da temperatura exibem picos que concordam qualitativamente com resultados experimentais. No limite de T &#8594 0 as taxas de relaxação são proporcionais a temperatura, mesmo nos casos em que efeitos de muitos corpos invalidam clássica derivação da lei de Korringa. O coeficiente linear é proporcional ao quadrado da suscetibilidade magnética à temperatura zero; isto generaliza a relação derivada por Shiba no limite Kondo. / The nuclear magnetic relaxation rate for an impurity in a metallic environment has been calculated as a function of temperature. Our calculations are based on the spin-degenerate Anderson model originally developed to describe dilute magnetic alloys. The relevance to heavy férmions, Valence fluctuation, and chemisorption on metallic surfaces is discussed. The temperature dependent rates exhibit peaks in qualitative agreement with experimental results. As expected, in the limit T &#8594 0 the rates are proportional to the temperature, even for cases in which many-body effects invalidate the classical derivation of the Korringa Law. The linear coefficient is shown to be proportional to the square of the zero temperature suscetibility; this generalizes a relation derived by Shiba in the Kondo limit.

In this work I present a 23Na/51V-NMR study of sodium vanadate as pure compound, and the influence of very small amounts of Sodium substitution by Calcium and Lithium is reported and discussed. The measurements of spin-lattice relaxation for 23Na and 51V are also presented. The sodium vanadate is found to have a double phase transition. The two transitions are close together and take place around 34 K. Above the transition temperature there is one V site in the mixed oxidation state 4.5+ and there is one Na site. A consistency for a number of un-doped and very slightly doped samples of three vanadium valences is argued, confirming a charge ordering transition at transition temperature, in good qualitative agreement with Bernert’s model and as well in quantitative and qualitative agreement with Sawa’s monoclinic structure. Below the transition temperature sodium is found to have ten sites. The number of the Na site is continuously developed with decreasing the temperature below transition temperature. This continues development of the Na sites demonstrates that the second transition is continues. The detailed spin-lattice relaxation rate for 23Na in both, the pure and the doped samples, in transition region, provided evidence for a non-symmetric and complex transition peak structure which we relate to the onset of more than one transition occurring at slightly different temperatures. This scales with the transition temperature reduction provided by lithium and calcium doping. The two transitions (i.e. dimerization and charge ordering) are intimately related. We investigated the spin-gap by means of Vanadium and Sodium spin-lattice relaxation temperature dependence well below transition temperature. The analysis of the single crystal data reveals a significant anisotropy in the nature of the gap, which is sensitive to Calcium and Lithium doping, indicating that is constrained to the ladder plane.

A taxa de relaxação magnética nuclear de uma impureza diluída em um meio metálico foi calculada como função da temperatura. Nossos cálculos são aplicados ao modelo de Anderson com degenerescência de spin, originalmente desenvolvido para descrever ligas magnéticas diluídas. Nossos cálculos são aplicados ao modelo de Anderson com degenerescência de spin, originalmente desenvolvido para descrever ligas magnéticas diluídas. Discutimos a relevância a sistemas de férmions pesados, valência flutuante e adsorção química em superfícies metálicas. As taxas de relaxação como função da temperatura exibem picos que concordam qualitativamente com resultados experimentais. No limite de T &#8594 0 as taxas de relaxação são proporcionais a temperatura, mesmo nos casos em que efeitos de muitos corpos invalidam clássica derivação da lei de Korringa. O coeficiente linear é proporcional ao quadrado da suscetibilidade magnética à temperatura zero; isto generaliza a relação derivada por Shiba no limite Kondo. / The nuclear magnetic relaxation rate for an impurity in a metallic environment has been calculated as a function of temperature. Our calculations are based on the spin-degenerate Anderson model originally developed to describe dilute magnetic alloys. The relevance to heavy férmions, Valence fluctuation, and chemisorption on metallic surfaces is discussed. The temperature dependent rates exhibit peaks in qualitative agreement with experimental results. As expected, in the limit T &#8594 0 the rates are proportional to the temperature, even for cases in which many-body effects invalidate the classical derivation of the Korringa Law. The linear coefficient is shown to be proportional to the square of the zero temperature suscetibility; this generalizes a relation derived by Shiba in the Kondo limit.

Realizamos medidas de tempos de relaxação de centros F em cristais de KCN, pela técnica de saturação do sinal de absorção por pulsos de microonda. Observamos um comportamento não exponencial para a recuperação da magnetização da amostra ap6so pulso. Este fato deve-se ao efeito combinado de relaxação cruzada ou difusão da magnetização pelo espectro de absorção, juntamente com a relaxação spin-rede. Medidas à 4,2 °K e 1,8 °K fornecem indícios que, ap6s algum tempo, apenas a relaxação spin-rede sobrexiste. O modelo teórico baseado na modulação da interação hiperfina e no processo direto fornece tempos menores que os obtidos experimentalmente. Isto deve-se à formação de conglomerados de centros. Também elaboramos um modelo levando em conta processo Raman, para prever tempos de relaxação spin-rede a temperaturas mais elevadas. / We measure the spin-lattice relaxation time of F centers in KCN at 1.8 and 4.2 K using the saturation recovery technique. The observed recovery is non exponential. This result is interpreted in terms of the combined effect of cross-relaxation and spin lattice relaxation. The values obtained for T1 (- sec) are found to be shorter than those calculated theoretically. This discrepancy is throught to arise from the presence of clusters. The characteristic time found from the initial part of recovery is found to be -6 sec in agreement with that found in KC for the recovery of a hole burnt in the resonance line (45). Finally the value of T1 was calculated for the Raman processes at high temperature and compared with known results.

In the past two decades polymer/clay nanocomposites (PCNs) have emerged as promising materials that exhibit remarkably improved properties when compared to conventional composites and pristine polymers. Such improvements strongly depend on the dispersion of clay nanoparticles in the polymer matrix. In spite of great efforts expended in characterizing clay dispersion, effective, simple and quantitative techniques are still needed. This work addresses this challenge by presenting new aspects of 1H solid-state NMR for quantifying clay dispersion in PCNs filled with clay containing paramagnetic ions. Employing these 1H solid-state NMR methods, some structure-processing-deformation relationships of PCNs were derived, and basic insights into nuclear relaxation and spin diffusion in PCNs were gained as well. Detailed models and analyses were described for 1H spin-lattice relaxation in the presence of paramagnetic clays in PCNs. Relaxation recovery was analytically correlated to clay dispersion in two ways: one is the initial relaxation recovery which is related to clay surface area, and the other is the spin-lattice relaxation time which is related to interparticle spacing. These two NMR observables were employed to quantitatively observe the evolution of clay morphology in poly(propylene)/clay (PP/MMT) nanocomposites upon equibiaxial stretching, as well as upon in situ uniaxial deformation. The initial relaxation recovery was independently utilized to determine the polymer-clay interfacial surface area and the degree of clay exfoliation. We demonstrated the capabilities of our models in quantitatively characterizing several materials, including poly(vinyl alcohol), nylon 6, poly(å-caprolactone) (PCL), poly(lactic acid) (PLA) and PP nanocomposites. These results were used to examine the dependence of clay morphology upon processing (strain ratio, strain rate, temperature), deformation (extension), component characteristics (polymer molecular weight, clay surface modification) and clay content. Effects of paramagnetic Fe3+ concentration and external magnetic field strength on 1H spin-lattice relaxation in PCNs were also investigated and discussed. In particular, low field separates the initial relaxation recovery into two stages: one related to clay content and the other related to the polymer-clay interfacial surface area. The low field was observed to enhance the paramagnetic contribution to the spin-lattice relaxation rate, increasing its sensitivity to clay morphology. In addition, measurements of long-distance spin diffusion coefficients for a variety of polymers and paramagnetic characteristics of organically modified clay were explored. Overall, the utility of NMR relaxometry in characterizing PCNs has been significantly expanded and successfully demonstrated in this dissertation.

Thesis (M.S.)--Mississippi State University. Department of Physics and Astronomy. / Title from title screen. Includes bibliographical references.