The correlation of structure and electronic properties near the surface of transition metal oxides

The strong couplings between different degrees of freedom are believed to be responsible for novel and complex phenomena discovered in transition metal oxides (TMOs). The physical complexity is directly responsible for their tunability. Creating surfaces/interfaces add an additional ' man-made' twist, approaching the quantum phenomena of correlated materials. ^ The dissertation focused on the structural and electronic properties in proximity of surface of three prototype TMO compounds by using three complementary techniques: scanning tunneling microscopy, angle-resolved photoelectron spectroscopy and low energy electron diffraction, particularly emphasized the effects of broken symmetry and imperfections like defects on the coupling between charge and lattice degrees of freedom. ^ Ca1.5Sr0.5RuO4 is a layered ruthenate with square lattice and at the boundary of magnetic/orbital instability in Ca2-xSrxRuO4. That the substitution of Sr 2+ with Ca2+ causing RuO6 rotation narrows the dxy band width and changes the Fermi surface topology. Particularly, the γ(dxy) Fermi surface sheet exhibited hole-like in Ca1.5Sr0.5RuO4 in contrast to electron-like in Sr2RuO4, showing a strong charge-lattice coupling. ^ Na0.75CoO2 is a layered cobaltite with triangular lattice exhibiting extraordinary thermoelectric properties. The well-ordered CoO2-terminated surface with random Na distribution was observed. However, lattice constants of the surface are smaller than that in bulk. The surface density of states (DOS) showed strong temperature dependence. Especially, an unusual shift of the minimum DOS occurs below 230 K, clearly indicating a local charging effect on the surface. ^ Cd2Re2O7 is the first known pyrochlore oxide superconductor (Tc ∼ 1K). It exhibited an unusual second-order phase transition occurring at TS1 = 200 K and a controversial first-order transition at TS2 = 120 K. While bulk properties display large anomalies at TS1 but rather subtle and sample-dependent changes at TS2, the surface DOS near the EF show no change at T s1 but a substantial increase below TS2---a complete reversal as the signature for the transitions. We argued that crystal imperfections, mainly defects, which were considerably enhanced at the surface, resulted in the transition at TS2. ^

Boundary Effects on Benthic Microbial Phosphorus Concentrations and Diatom Beta Diversity in a Hydrologically-modified, Nutrient-limited Wetland

Water flow and flooding duration in wetlands influence the structure and productivity of microbial communities partly through their influence on nutrient loading. The effect of flow-regulated nutrient loads is especially relevant for microbial communities in nutrient-poor settings, where delivery controls nutrient uptake rates and the intensity of microbial interactions. We examined the effect of hydrologic history and proximity to water sources on nutrient enrichment of benthic microbial assemblages (periphyton) and on their diatom species composition, along the artificial boundaries of Taylor Slough, a historically phosphorus-depleted drainage of the Florida Everglades. Concentrations of phosphorus in periphyton declined from the wetland boundary near inflow structures to 100-m interior, with spatial and temporal variability in rates dependent on proximity to and magnitude of water flow. Phosphorus availability influenced the beta diversity of diatom assemblages, with higher values near inflow structures where resources were greatest, while interior sites and reference transects contained assemblages with constant composition of taxa considered endemic to the Everglades. This research shows how hydrologic restoration may have unintended consequences when incoming water quality is not regulated, including a replacement of distinctive microbial assemblages by ubiquitous, cosmopolitan ones.

Metacommunity Structure Along Resource and Disturbance Gradients in Everglades Wetlands

We evaluated metacommunity hypotheses of landscape arrangement (indicative of dispersal limitation) and environmental gradients (hydroperiod and nutrients) in structuring macroinvertebrate and fish communities in the southern Everglades. We used samples collected at sites from the eastern boundary of the southern Everglades and from Shark River Slough, to evaluate the role of these factors in metacommunity structure. We used eigenfunction spatial analysis to model community structure among sites and distance-based redundancy analysis to partition the variability in communities between spatial and environmental filters. For most animal communities, hydrological parameters had a greater influence on structure than nutrient enrichment, however both had large effects. The influence of spatial effects indicative of dispersal limitation was weak and only periphyton infauna appeared to be limited by regional dispersal. At the landscape scale, communities were well-mixed, but strongly influenced by hydrology. Local-scale species dominance was influenced by water-permanence and nutrient enrichment. Nutrient enrichment is limited to water inflow points associated with canals, which may explain its impact in this data set. Hydroperiod and nutrient enrichment are controlled by water managers; our analysis indicates that the decisions they make have strong effects on the communities at the base of the Everglades food web.

Boundary : an exploration of architecture's power to mark a boundary

Cities are no longer recognizing their boundaries beyond their legal or political implications. This thesis explored the architecture of a boundary in the design of a structure that visually and symbolically marked the current Miami-Dade County development limit along Krome Avenue. This limit ultimately separates the city from the endangered Everglades ecosystem. Through the examination of ancient boundaries such as Medieval and Renaissance Military fortifications, as well as contemporary interventions such as Steven Holl's "Edge of the City Projects", an architectural vocabulary was developed considering the Double Wall, Bastion, Rampart, and Gate principles. However, rather than considering these principles to defend the city from outside forces, the focus of this exploration is their inversion in order to contain the city by strengthening its periphery visually and symbolically. From this exploration, it was concluded that a successful boundary or limit should be visible and significant. Furthermore, it should serve as an informative and reflective landmark.

Development of a Coupling Model for Fluid-Structure Interaction using the Mesh-free Finite Element Method and the Lattice Boltzmann Method

In the presented thesis work, the meshfree method with distance fields was coupled with the lattice Boltzmann method to obtain solutions of fluid-structure interaction problems. The thesis work involved development and implementation of numerical algorithms, data structure, and software. Numerical and computational properties of the coupling algorithm combining the meshfree method with distance fields and the lattice Boltzmann method were investigated. Convergence and accuracy of the methodology was validated by analytical solutions. The research was focused on fluid-structure interaction solutions in complex, mesh-resistant domains as both the lattice Boltzmann method and the meshfree method with distance fields are particularly adept in these situations. Furthermore, the fluid solution provided by the lattice Boltzmann method is massively scalable, allowing extensive use of cutting edge parallel computing resources to accelerate this phase of the solution process. The meshfree method with distance fields allows for exact satisfaction of boundary conditions making it possible to exactly capture the effects of the fluid field on the solid structure.