Results of spin density functional theory (SDFT) calculations were used to construct and check features of a generally applicable semi-quantitative approach to understanding magnetic coupling in gadolinium-containing molecules, clusters, and solids. Using fragments based on structures of metal-rich lanthanide compounds, we have investigated molecular and low-dimensional extended structures, and have shown that open-d-shell clusters facilitate strong ferromagnetic coupling whereas closed-d-shell systems prefer antiferromagnetic coupling. The qualitative features can be interpreted using a perturbative molecular orbital (PMO) model that focuses the influence of the 4f 7- d exchange interaction on the d-based molecular orbitals. The f-d exchange interaction, mediated by spin polarization of both filled and partially-filled metal-metal bonding orbitals, is described for the model system Gd3I6(OPH3)12 n+ using basic perturbation methods. This approach is successful for predicting the magnetic ground state for Gd2Cl3, a semiconducting system for which calculations predict antiferromagnetic ordering of the 4f 7 moments in a pattern consistent with published neutron diffraction data. An attempt to account for the calculated magnetic energies of spin patterns using an Ising model was unsuccessful, indicating that the Ising model is inappropriate. Instead, the d-electron mediated f-f exchange interaction was interpreted using our basic perturbation theory approach. Computed density of states and spin polarization information was used to support the perturbation-theoretic analysis. This method has also been successful evaluating the ground state for Gd[Gd6FeI12]. Using the model [Gd6CoI12](OPH3)6, which has three unpaired electrons in the HOMO, the 4f moments prefer spin alignment with the unpaired electrons in the system and the ferromagnetic 4f 7 spin arrangement is the ground state. We have extended our analysis of R6X12 clusters to include nonmetal interstitial atoms, the bioctahedral cluster compounds Gd10Cl17C4 and Gd10I16C4, and Gd5(O)(OPri)5. Finally, we have shown that we can successfully predict the ground state magnetic structures of several metallic and semiconducting Gd-containing compounds, Gd2Cl3, GdB2C2,alpha-Gd2S3, Gd5Si4, and Gd5Ge4, using semi-empirical calculations which closely simulates the exchange effects exerted by the 4f electrons. In a more speculative vein, ideas concerning the incorporation of anisotropic rare-earth metal atoms to the cluster framework are touched upon.

minerology

Thesis (Ph. D.)--Rutgers University, 2009. / "Graduate Program in Ceramic and Materials Science and Engineering." Includes bibliographical references.

Thesis (M.S.)--Miami University, Dept. of Geology, 2001. / Title from first page of PDF document. Document formatted into pages; contains viii, 150 p. : ill. Includes bibliographical references.

Thesis (Ph. D.)--University of Queensland, 2002. / Includes bibliographical references.

Thesis (Ph. D.)--University of Washington, 2003. / Vita. Includes bibliographical references (p. 109-117).

Thesis--Ph. D., University of Hong Kong, 1987.

Atmospheric noble gases (He, Ne, Ar, Kr, and Xe) dissolved in groundwater are a valuable tool in hydrology. Numerous studies have relied on groundwater recharge temperatures calculated from dissolved noble gas data (noble gas temperatures, NGT) to infer paleoclimate conditions. This research investigated gas dissolution during groundwater recharge and critically examined the use of dissolved noble gas data in groundwater research. A detailed investigation of an agriculturally impacted shallow aquifer allowed comparison of measured water table temperatures (WTT) with calculated NGT. Results suggest that NGT calculated from widely used noble gas interpretive models do reflect measured WTT, supporting the use of dissolved noble gases to deduce recharge temperatures. Samples having dissolved gas concentrations below the equilibrium concentration with respect to atmospheric pressure were attributed to denitrification induced gas stripping in the saturated zone. Modeling indicated that minor degassing (<10% [Delta]Ne) may cause underestimation of groundwater recharge temperature by up to 2 °C. In another study a large dissolved noble gas data set (905 samples) from California was analyzed. Noble gas modeling using the same interpretive models indicates that multiple models may fit measured data within measurement uncertainty, suggesting that goodness-of-fit is not a robust indicator of model appropriateness. A unique aspect of this study was the high Ne and excess air concentrations associated with surficial artificial recharge facilities. A final study examined whether climatic/hydrologic changes occurring over glacial-interglacial time periods could impact the accuracy of NGT used in paleoclimate studies. Numerical modeling experiments estimated WTT sensitivity to changes in: 1) precipitation amount, 2) water table depth, and 3) air temperature. Precipitation and water table depth had a minor impact on WTT (~0.2 °C). In contrast, the impact of air temperature changes on WTT was more pronounced. Results suggest that air temperatures inferred from NGT data may underestimate actual air temperature change since the last glacial maximum by ~1 °C at sites having seasonal snowcover. These results suggest despite uncertainty in the exact physical processes controlling gas dissolution during groundwater recharge, NGT do reflect WTT. However, inferring paleo-air temperatures from NGT are subject to error, especially locations with seasonal snowcover. / text

Performing simulations of large-scale bio-molecular systems has long been one of the great challenges of molecular biophysics. Phenomena, such as the folding and conformational rearrangement of proteins, often takes place over the course milliseconds-to-seconds. The methods of traditional molecular dynamics used to simulate such systems are on the other hand typically limited to giving trajectories of nanosecond-to-microsecond duration. The failure of traditional methods has thus motivated the development of many special purpose techniques that propose to capture the essential characteristics of systems over conventionally inaccessible timescales. This dissertation first focuses on presenting a set of advances made on one such technique, Milestoning. Milestoning gives a statistical procedure for recovering long trajectories of the system based on observations of many short trajectories that start and end on hypersurfaces in the system’s phase space. Justification of the method’s validity typically relies on the assumption that trajectories of the system lose all memory between crossing successive milestones. We start by giving a modified milestoning procedure in which both the memory loss assumption is relaxed and reaction mechanisms are more easily extracted. We follow with numerical examples illustrating the success of new procedure. Then we show how milestoning may be used to compute an experimentally relevant timescale known as the transit time (also known as the reaction path time). Finally, we discuss how time reversal symmetry may be exploited to improve sampling of the trajectory fragments that connect milestones. After discussing milestoning, the dissertation shifts focus to a different way of approaching the problem of simulating long timescales. We consider two polymers models that are sufficiently simple to permit numerical integration of the desired long trajectories of the system. In some limiting cases, we see their simplicity even permits some questions about the dynamcis to be answered analytically. Using these models, we make a series of experimentally verifiable predictions about the dynamics of unfolded polymers. / text

published_or_final_version / Electrical and Electronic Engineering / Master / Master of Philosophy