I. Thermochemistry and reaction kinetics of disolvated protons by ion cyclotron resonance spectroscopy. II. Thermochemical studies of small fluorocarbons by photoionization mass spectrometry

The disolvated proton, H(OH₂)₂⁺ is employed as a chemical reagent in low pressure (˂ 10^-5 torr) investigations by ion cyclotron resonance spectroscopy. Since termolecular reactions are absent at low pressure, disolvated protons are not generally observed. However H(OH₂)₂⁺ is produced in a sequence of bimolecular reactions in mixtures containing H₂O and one of a small number of organohalide precursors. Then a series of hydrated Lewis bases is produced by H₃O⁺ transfer from H(OH₂)₂⁺. In Chapter II, the relative stability of hydrated bases containing heteroatoms of both first and second row elements is determined from the preferred direction of H₃O⁺ transfer between BH(OH₂)⁺ complexes. S and P containing bases are shown to bind H₃O⁺ more weakly than O and N bases with comparable proton affinities. A simple model of hydrogen bonding is proposed to account for these observations.

H⁺ transfer from H(OH₂)₂⁺ to several Lewis bases also occurs at low pressure. In Chapter III the relative importance of H₃O⁺ transfer and H⁺ transfer from H(OH₂)₂⁺ to a series of bases is observed to be a function of base strength. Beginning with CH₃COOH, the weakest base for which H⁺ transfer is observed, the importance of H⁺ transfer increases with increasing proton affinity of the acceptor base. The nature of neutral products formed from H(OH₂)₂⁺ by loss of H⁺ is also considered.

Chapters IV and V deal with thermochemistry of small fluorocarbons determined by photoionization mass spectrometry. The enthalpy of formation of CF₂ is considered in Chapter IV. Photoionization of perfluoropropylene, perfluorocyclopropane, and trifluoromethyl benzene yield onsets for ions formed by loss of a CF₂ neutral fragment. Earlier determinations of ΔH^°_f298 (CF₂) are reinterpreted using updated thermochemical values and compared with results of this study. The heat of formation of neutral perfluorocyclopropane is also derived. Finally, the energetics of interconversion of perfluoropropylene and perfluorocyclopropane are considered for both the neutrals and their molecular ions.

In Chapter V the heats of formation of CF₃⁺ and CF₃I⁺are derived from photoionization of CF₃I. These are considered with respect to ion-molecule reactions observed in CF₃I monitored by the techniques of ion cyclotron resonance spectroscopy. Results obtained in previous experiments are also compared.

Measurement of small vibration amplitudes of a rough surface by an interferometer with a self-pumped phase-conjugate mirror

The application of a Michelson interferometer with a self-pumped phase-conjugate mirror to measure small vibration amplitudes of a rough surface is described. The distorted wave front of the light that is diffusely reflected from the rough surface is restored by phase conjugation to provide an interference signal with a high signal-to-noise ratio. The vibration amplitudes of a stainless-steel sample are measured with a precision of similar to 5 nm. (C) 2000 Optical Society of America OCIS codes: 120.3180, 190.5040, 120.7280.

Small-dynamic-angle measurement using tangent relationship and phase-modulating technique

A method using two prisms for measurement of small dynamic angles is proposed in which the measurement is based on a simple tangent equation and a phase-modulating interferometer with a laser diode to measure dynamic optical path differences with higher accuracy. Owing to the simple tangent equation, the symmetry requirement on the two prisms in the optical configuration is eliminated, and easy measurement of the separations between two parallel beams with a position-sensitive detector is achieved. Small-dynamic-angle measurements are experimentally demonstrated with high accuracy. (C) 2007 Society of Photo-Optical Instrumentation Engineers.

Small-dynamic-angle measurement using tangent relationship and phase-modulating technique

A method using two prisms for measurement of small dynamic angles is proposed in which the measurement is based on a simple tangent equation and a phase-modulating interferometer with a laser diode to measure dynamic optical path differences with higher accuracy. Owing to the simple tangent equation, the symmetry requirement on the two prisms in the optical configuration is eliminated, and easy measurement of the separations between two parallel beams with a position-sensitive detector is achieved. Small-dynamic-angle measurements are experimentally demonstrated with high accuracy. (C) 2007 Society of Photo-Optical Instrumentation Engineers.

Coma measurement of projection optics in lithographic tools based on relative image displacements at multiple illumination settings

In this paper, we propose a novel method for measuring the coma aberrations of lithographic projection optics based on relative image displacements at multiple illumination settings. The measurement accuracy of coma can be improved because the phase-shifting gratings are more sensitive to the aberrations than the binary gratings used in the TAMIS technique, and the impact of distortion on displacements of aerial image can be eliminated when the relative image displacements are measured. The PROLITH simulation results show that, the measurement accuracy of coma increases by more than 25% under conventional illumination, and the measurement accuracy of primary coma increases by more than 20% under annular illumination, compared with the TAMIS technique. (c) 2007 Optical Society of America.

The Design and Synthesis of Transition Metal Complexes Supported by Non-innocent Ligand Scaffolds for Small Molecule Activation

This dissertation focuses on the incorporation of non-innocent or multifunctional moieties into different ligand scaffolds to support one or multiple metal centers in close proximity. Chapter 2 focuses on the initial efforts to synthesize hetero- or homometallic tri- or dinuclear metal carbonyl complexes supported by para-terphenyl diphosphine ligands. A series of [M₂M’(CO)₄]-type clusters (M = Ni, Pd; M’ = Fe, Co) could be accessed and used to relate the metal composition to the properties of the complexes. During these studies it was also found that non-innocent behavior was observed in dinuclear Fe complexes that result from changes in oxidation state of the cluster. These studies led to efforts to rationally incorporate central arene moieties capable managing both protons and electrons during small molecule activation.

Chapter 3 discusses the synthesis of metal complexes supported by a novel para-terphenyl diphosphine ligand containing a non-innocent 1,4-hydroquinone moiety as the central arene. A Pd⁰-hydroquinone complex was found to mediate the activation of a variety of small molecules to form the corresponding Pd⁰-quinone complexes in a formal two proton ⁄ two electron transformation. Mechanistic investigations of dioxygen activation revealed a metal-first activation process followed by subsequent proton and electron transfer from the ligand. These studies revealed the capacity of the central arene substituent to serve as a reservoir for a formal equivalent of dihydrogen, although the stability of the M-quinone compounds prevented access to the PdII-quinone oxidation state, thus hindering of small molecule transformations requiring more than two electrons per equivalent of metal complex.

Chapter 4 discusses the synthesis of metal complexes supported by a ligand containing a 3,5-substituted pyridine moiety as the linker separating the phenylene phosphine donors. Nickel and palladium complexes supported by this ligand were found to tolerate a wide variety of pyridine nitrogen-coordinated electrophiles which were found to alter central pyridine electronics, and therefore metal-pyridine π-system interactions, substantially. Furthermore, nickel complexes supported by this ligand were found to activate H-B and H-Si bonds and formally hydroborate and hydrosilylate the central pyridine ring. These systems highlight the potential use of pyridine π-system-coordinated metal complexes to reversibly store reducing equivalents within the ligand framework in a manner akin to the previously discussed 1,4-hydroquinone diphosphine ligand scaffold.

Chapter 5 departs from the phosphine-based chemistry and instead focuses on the incorporation of hydrogen bonding networks into the secondary coordination sphere of [Fe₄(μ₄-O)]-type clusters supported by various pyrazolate ligands. The aim of this project is to stabilize reactive oxygenic species, such as oxos, to study their spectroscopy and reactivity in the context of complicated multimetallic clusters. Herein is reported this synthesis and electrochemical and Mössbauer characterization of a series of chloride clusters have been synthesized using parent pyrazolate and a 3-aminophenyl substituted pyrazolate ligand. Efforts to rationally access hydroxo and oxo clusters from these chloride precursors represents ongoing work that will continue in the group.

Appendix A discusses attempts to access [Fe₃Ni]-type clusters as models of the enzymatic active site of [NiFe] carbon monoxide dehydrogenase. Efforts to construct tetranuclear clusters with an interstitial sulfide proved unsuccessful, although a (μ₃-S) ligand could be installed through non-oxidative routes into triiron clusters. While [Fe₃Ni(μ₄-O)]-type clusters could be assembled, accessing an open heterobimetallic edge site proved challenging, thus prohibiting efforts to study chemical transformations, such as hydroxide attack onto carbon monoxide or carbon dioxide coordination, relevant to the native enzyme. Appendix B discusses the attempts to synthesize models of the full H-cluster of [FeFe]-hydrogenase using a bioinorganic approach. A synthetic peptide containing three cysteine donors was successfully synthesized and found to chelate a preformed synthetic [Fe₄S₄] cluster. However, efforts to incorporate the diiron subsite model complex proved challenging as the planned thioester exchange reaction was found to non-selectively acetylate the peptide backbone, thus preventing the construction of the full six-iron cluster.

Ecological indicators of water quality in small rivers

At the present time hydrobiological indicators are widely used for the control of surface water quality. Results of the applying of methods suggested at the 1st Soviet-American seminar (1975), development of improved methods and estimation of their usefulness for various conditions are presented in this report. Among the criteria permitting an estimation of the degree and character of changes in water quality and their connection with the functioning of river ecosystems in general, the biological tests of natural waters appears to be the most universal one and is being carried out in two main directions — ecological and physiological. This study summarises approaches in both directions.

Small scale turbulence in high Karlovitz number premixed flames

The purpose of this thesis is to characterize the behavior of the smallest turbulent scales in high Karlovitz number (Ka) premixed flames. These scales are particularly important in the two-way coupling between turbulence and chemistry and better understanding of these scales will support future modeling efforts using large eddy simulations (LES). The smallest turbulent scales are studied by considering the vorticity vector, ω, and its transport equation.

Due to the complexity of turbulent combustion introduced by the wide range of length and time scales, the two-dimensional vortex-flame interaction is first studied as a simplified test case. Numerical and analytical techniques are used to discern the dominate transport terms and their effects on vorticity based on the initial size and strength of the vortex. This description of the effects of the flame on a vortex provides a foundation for investigating vorticity in turbulent combustion.

Subsequently, enstrophy, ω² = ω • ω, and its transport equation are investigated in premixed turbulent combustion. For this purpose, a series of direct numerical simulations (DNS) of premixed n-heptane/air flames are performed, the conditions of which span a wide range of unburnt Karlovitz numbers and turbulent Reynolds numbers. Theoretical scaling analysis along with the DNS results support that, at high Karlovitz number, enstrophy transport is controlled by the viscous dissipation and vortex stretching/production terms. As a result, vorticity scales throughout the flame with the inverse of the Kolmogorov time scale, τ_η, just as in homogeneous isotropic turbulence. As τ_η is only a function of the viscosity and dissipation rate, this supports the validity of Kolmogorov’s first similarity hypothesis for sufficiently high Ka numbers (Ka ≳ 100). These conclusions are in contrast to low Karlovitz number behavior, where dilatation and baroclinic torque have a significant impact on vorticity within the flame. Results are unaffected by the transport model, chemical model, turbulent Reynolds number, and lastly the physical configuration.

Next, the isotropy of vorticity is assessed. It is found that given a sufficiently large value of the Karlovitz number (Ka ≳ 100) the vorticity is isotropic. At lower Karlovitz numbers, anisotropy develops due to the effects of the flame on the vortex stretching/production term. In this case, the local dynamics of vorticity in the strain-rate tensor, S, eigenframe are altered by the flame. At sufficiently high Karlovitz numbers, the dynamics of vorticity in this eigenframe resemble that of homogeneous isotropic turbulence.

Combined, the results of this thesis support that both the magnitude and orientation of vorticity resemble the behavior of homogeneous isotropic turbulence, given a sufficiently high Karlovitz number (Ka ≳ 100). This supports the validity of Kolmogorov’s first similarity hypothesis and the hypothesis of local isotropy under these condition. However, dramatically different behavior is found at lower Karlovitz numbers. These conclusions provides/suggests directions for modeling high Karlovitz number premixed flames using LES. With more accurate models, the design of aircraft combustors and other combustion based devices may better mitigate the detrimental effects of combustion, from reducing CO₂ and soot production to increasing engine efficiency.

Changes of water quality and sediment phosphorus of a small productive lake following decreased phosphorus loading

Esthwaite Water is the most productive or eutrophic lake in the English Lake District. Since 1945 its water quality has been determined from weekly or biweekly measurements of temperature, oxygen, plant nutrients and phytoplankton abundance. The lake receives phosphorus from its largely lowland-pasture catchment, sewage effluent from the villages of Hawkshead and Near Sawrey, and from a cage-culture fish farm. From 1986 phosphorus has been removed from the sewage effluent of Hawkshead which was considered to contribute between 47% and 67% of the total phosphorus loading to the lake. At the commencement of phosphorus removal regular measurements of phosphorus in the superficial 0-4 cm layer of lake sediment were made from cores collected at random sites. Since 1986 the mean annual concentration of alkali-extractable sediment phosphorus has decreased by 23%. This change is not significant at the 5% level but nearly so. There has been no marked change in water quality over this period. Summer dominance of blue-green algae which arose in the early 1980s after decline of the previous summer forms, Ceratium spp., has been maintained. Improvement in water quality is unlikely to be achieved at the present phosphorus loading.

Picophytoplankton in freshwater ecosystems: the importance of small-sized phototrophs

About 40 years have passed since the discovery of picophytoplankton; the present knowledge of the taxonomy, physiology and ecology of these tiny photoautotrophic cells offers new perspectives on the importance of the microbial contribution to global biogeochemical cycles and food webs. This review focuses on the relationships among the components of picophytoplankton (picocyanobacteria and the picoplanktic eukaryotes) and biotic and abiotic environmental factors. The dynamics of picophytoplankton in aquatic ecosystems are strictly dependent upon basin size and trophy, temperature, and nutrient and light limitation, but they are also regulated by grazing and viral-induced lysis. The review considers: the pros and cons of the molecular approach to the study of the taxonomy of freshwater Synechococcus spp.; the importance of ecological aspects in understanding the puzzle of picophytoplankton phylogeny (genotype vs ecotype); and the role of biotic vs abiotic interactions in controlling picophytoplankton dynamics. Biotic, top-down control mechanisms are reviewed as well as knowledge of other biological interactions.

Picophytoplankton in freshwater ecosystems: the importance of small-sized phototrophs

About 40 years have passed since the discovery of picophytoplankton; the present knowledge of the taxonomy, physiology and ecology of these tiny photoautotrophic cells offers new perspectives on the importance of the microbial contribution to global biogeochemical cycles and food webs. This review focuses on the relationships among the components of picophytoplankton (picocyanobacteria and the picoplanktic eukaryotes) and biotic and abiotic environmental factors. The dynamics of picophytoplankton in aquatic ecosystems are strictly dependent upon basin size and trophy, temperature, and nutrient and light limitation, but they are also regulated by grazing and viral-induced lysis. The review considers: the pros and cons of the molecular approach to the study of the taxonomy of freshwater Synechococcus spp.; the importance of ecological aspects in understanding the puzzle of picophytoplankton phylogeny (genotype vs ecotype); and the role of biotic vs abiotic interactions in controlling picophytoplankton dynamics. Biotic, top-down control mechanisms are reviewed as well as knowledge of other biological interactions.