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. ^

Hydrological dynamics between a coastal aquifer and the adjacent estuarine system, Biscayne Bay, South Florida

Geochemical and geophysical approaches have been used to investigate the freshwater and saltwater dynamics in the coastal Biscayne Aquifer and Biscayne Bay. Stable isotopes of oxygen and hydrogen, and concentrations of Sr2+ and Ca2+ were combined in two geochemical mixing models to provide estimates of the various freshwater inputs (precipitation, canal water, and groundwater) to Biscayne Bay and the coastal canal system in South Florida. Shallow geophysical electromagnetic and direct current resistivity surveys were used to image the geometry and stratification of the saltwater mixing zone in the near coastal (less than 1km inland) Biscayne Aquifer. The combined stable isotope and trace metal models suggest a ratio of canal input-precipitation-groundwater of 38%–52%–10% in the wet season and 37%–58%–5% in the dry season with an error of 25%, where most (20%) of the error was attributed to the isotope regression model, while the remaining 5% error was attributed to the Sr2+/Ca2+ mixing model. These models suggest rainfall is the dominate source of freshwater to Biscayne Bay. For a bay-wide water budget that includes saltwater and freshwater mixing, fresh groundwater accounts for less than 2% of the total input. A similar Sr 2+/Ca2+ tracer model indicates precipitation is the dominate source in 9 out of 10 canals that discharge into Biscayne Bay. The two-component mixing model converged for 100% of the freshwater canal samples in this study with 63% of the water contributed to the canals coming from precipitation and 37% from groundwater inputs ±4%. There was a seasonal shift from 63% precipitation input in the dry season to 55% precipitation input in the wet season. The three end-member mixing model converged for only 60% of the saline canal samples possibly due to non-conservative behavior of Sr2+ and Ca2+ in saline groundwater discharging into the canal system. Electromagnetic and Direct Current resistivity surveys were successful at locating and estimating the geometry and depth of the freshwater/saltwater interface in the Biscayne Aquifer at two near coastal sites. A saltwater interface that deepened as the survey moved inland was detected with a maximum interpreted depth to the interface of 15 meters, approximately 0.33 km inland from the shoreline. ^