In Part 1, geometric clusters of the Ising model are studied as possible model clusters for nuclear multifragmentation. These clusters may not be considered as non-interacting (ideal gas) due to excluded volume effect which predominantly is the artifact of the cluster's finite size. Interaction significantly complicates the use of clusters in the analysis of thermodynamic systems. Stillinger's theory is used as a basis for the analysis, which within the RFL (Reiss, Frisch, Lebowitz) fluid-of-spheres approximation produces a prediction for cluster concentrations well obeyed by geometric clusters of the Ising model. If thermodynamic condition of phase coexistence is met, these concentrations can be incorporated into a differential equation procedure of moderate complexity to elucidate the liquid-vapor phase diagram of the system with cluster interaction included. The drawback of increased complexity is outweighted by the reward of greater accuracy of the phase diagram, as it is demonstrated by the Ising model. A novel nuclear-cluster analysis procedure is developed by modifying Fisher's model to contain cluster interaction and employing the differential equation procedure to obtain thermodynamic variables. With this procedure applied to geometric clusters, the guidelines are developed to look for excluded volume effect in nuclear multifragmentation. In part 2, an explanation is …

Sum frequency generation (SFG) vibrational spectroscopy, atomic force microscopy (AFM), and quartz crystal microbalance (QCM) have been used to study the molecular surface structure, surface topography and mechanical properties, and quantitative adsorbed amount of biological molecules at the solid-liquid interface. The molecular-level behavior of designed peptides adsorbed on hydrophobic polystyrene and hydrophilic silica substrates has been examined as a model of protein adsorption on polymeric biomaterial surfaces. Proteins are such large and complex molecules that it is difficult to identify the features in their structure that lead to adsorption and interaction with solid surfaces. Designed peptides which possess secondary structure provide simple model systems for understanding protein adsorption. Depending on the amino acid sequence of a peptide, different secondary structures ({alpha}-helix and {beta}-sheet) can be induced at apolar (air/liquid or air/solid) interfaces. Having a well-defined secondary structure allows experiments to be carried out under controlled conditions, where it is possible to investigate the affects of peptide amino acid sequence and chain length, concentration, buffering effects, etc. on adsorbed peptide structure. The experiments presented in this dissertation demonstrate that SFG vibrational spectroscopy can be used to directly probe the interaction of adsorbing biomolecules with a surface or interface. The use of …

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Manganese model complexes, relevant to the oxygen-evolving complex (OEC) in photosynthesis, were studied with Mn K-edge X-ray absorption near-edge spectroscopy (XANES), Mn Kb X-ray emission spectroscopy (XES), and vibrational spectroscopy. A more detailed understanding was obtained of the influence of nuclearity, overall structure, oxidation state, and ligand environment of the Mn atoms on the spectra from these methods. This refined understanding is necessary for improving the interpretation of spectra of the OEC. Mn XANES and Kb XES were used to study a di-(mu)-oxo and a mono-(mu)-oxo di-nuclear Mn compound in the (III,III), (III,IV), and (IV,IV) oxidation states. XANES spectra show energy shifts of 0.8 - 2.2 eV for 1-electron oxidation-state changes and 0.4 - 1.8 eV for ligand-environment changes. The shifts observed for Mn XES spectra were approximately 0.21 eV for oxidation state-changes and only approximately 0.04 eV for ligand-environment changes. This indicates that Mn Kb XES i s more sensitive to the oxidation state and less sensitive to the ligand environment of the Mn atoms than XANES. These complimentary methods provide information about the oxidation state and the ligand environment of Mn atoms in model compounds and biological systems. A versatile spectroelectrochemical apparatus was designed to aid the interpretation …