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Groundwater flow paths and processes that govern metal mobility and transport are difficult to characterize in mountainous bedrock watersheds. Despite the difficulty in holistic characterization, conceptual understanding of subsurface hydrologic and geochemical processes is key to developing remediation plans for locations affected by acid mine drainage, such as the Upper Animas River watershed in southwestern Colorado, USA. Stable isotopes of water and rare earth elements were utilized to evaluate groundwater flow and metal sources within this complex catchment. Stable isotope samples collected from draining mine adits and springs display systematic spatial variation wherein sample sites at higher elevations have greater seasonal variability than sites at lower elevations. The Upper Cement Creek watershed, where multiple draining mines are present, displays the lowest seasonal variation in stable isotopic signatures, potentially indicating the presence of a large, well-mixed volume of groundwater storage or interbasin groundwater flow. Rare earth elements display statistically significant variation between different alteration styles in the catchment. Overprinting of regional propylitic alteration is evident based on enrichment of middle rare earth elements in acidic springs and mines that are not spatially associated with surficial exposures of acid generating alteration styles. Europium anomaly and middle rare earth enrichment signatures from two flooded mine tunnels on opposite sides of a watershed divide indicate connections to the same subsurface flooded mine workings. 

Atomistic molecular dynamics (MD) simulations of ordered and disordered P3HT at varying temperatures reveal distinct thermomechanical behavior in the amorphous and crystalline material domains. 

Spontaneous Ge₆O₈cluster formation under ambient conditions using dispersion enhanced aryloxo ligands. 

Linear and nonlinear optical lineshapes reveal details of excitonic structure in semiconductor polymers. We implement absorption, photoluminescence, and transient absorption spectroscopies in DPP-DTT, an electron push-pull copolymer, to explore the relationship between their spectral lineshapes and chain conformation, deduced from resonance Raman spectroscopy and from ab initio calculations. The viscosity of precursor polymer solutions before film casting displays a transition that suggests gel formation above a critical concentration. Upon crossing this viscosity deflection concentration, the lineshape analysis of the absorption spectra within a photophysical aggregate model reveals a gradual increase in interchain excitonic coupling. We also observe a red-shifted and line-narrowed steady-state photoluminescence spectrum, along with increasing resonance Raman intensity in the stretching and torsional modes of the dithienothiphene unit, which suggests a longer exciton coherence length along the polymer-chain backbone. Furthermore, we observe a change of lineshape in the photoinduced absorption component of the transient absorption spectrum. The derivative-like lineshape may originate from two possibilities: a new excited-state absorption, or from Stark effect, both of which are consistent with the emergence of high-energy shoulder as seen in both photoluminescence and absorption spectra. Therefore, we conclude that the exciton is more dispersed along the polymer chain backbone with increasing concentrations, leading to the hypothesis that the polymer chain order is enhanced when the push-pull polymers are processed at higher concentrations. Thus, tuning the microscopic chain conformation by concentration would be another factor of interest when considering the polymer assembly pathways for pursuing large-area and high-performance organic optoelectronic devices.