I. The crystal structure of potassium bis(tricyanovinyl)amine. II. Nuclear magnetic resonance studies of alkali halide solutions. III. Elucidation of the intramolecular hydrogen bond in acetylacetone by the deuterium isotope effect on the chemical shift of the bridge hydrogen

Part I

Potassium bis-(tricyanovinyl) amine, K⁺N[C(CN)=C(CN)₂]₂^-, crystallizes in the monoclinic system with the space group Cc and lattice constants, a = 13.346 ± 0.003 Å, c = 8.992 ± 0.003 Å, B = 114.42 ± 0.02°, and Z = 4. Three dimensional intensity data were collected by layers perpendicular to b* and c* axes. The crystal structure was refined by the least squares method with anisotropic temperature factor to an R value of 0.064.

The average carbon-carbon and carbon-nitrogen bond distances in –C-CΞN are 1.441 ± 0.016 Å and 1.146 ± 0.014 Å respectively. The bis-(tricyanovinyl) amine anion is approximately planar. The coordination number of the potassium ion is eight with bond distances from 2.890 Å to 3.408 Å. The bond angle C-N-C of the amine nitrogen is 132.4 ± 1.9°. Among six cyano groups in the molecule, two of them are bent by what appear to be significant amounts (5.0° and 7.2°). The remaining four are linear within the experimental error. The bending can probably be explained by molecular packing forces in the crystals.

Part II

The nuclear magnetic resonance of ⁸¹Br and ¹²⁷I in aqueous solutions were studied. The cation-halide ion interactions were studied by studying the effect of the Li⁺, Na⁺, K⁺, Mg⁺⁺, Cs⁺ upon the line width of the halide ions. The solvent-halide ion interactions were studied by studying the effects of methanol, acetonitrile, and acetone upon the line width of ⁸¹Br and ¹²⁷I in the aqueous solutions. It was found that the viscosity plays a very important role upon the halide ions line width. There is no specific cation-halide ion interaction for those ions such as Mg⁺⁺, Di⁺, Na⁺, and K⁺, whereas the Cs⁺ - halide ion interaction is strong. The effect of organic solvents upon the halide ion line width in aqueous solutions is in the order acetone ˃ acetonitrile ˃ methanol. It is suggested that halide ions do form some stable complex with the solvent molecules and the reason Cs⁺ can replace one of the ligands in the solvent-halide ion complex.

Part III

An unusually large isotope effect on the bridge hydrogen chemical shift of the enol form of pentanedione-2, 4(acetylacetone) and 3-methylpentanedione-2, 4 has been observed. An attempt has been made to interpret this effect. It is suggested from the deuterium isotope effect studies, temperature dependence of the bridge hydrogen chemical shift studies, IR studies in the OH, OD, and C=O stretch regions, and the HMO calculations, that there may probably be two structures for the enol form of acetylacetone. The difference between these two structures arises mainly from the electronic structure of the π-system. The relative population of these two structures at various temperatures for normal acetylacetone and at room temperature for the deuterated acetylacetone were calculated.

Periodic solutions of integro-differential equations which arise in population dynamics

The problem of the existence and stability of periodic solutions of infinite-lag integra-differential equations is considered. Specifically, the integrals involved are of the convolution type with the dependent variable being integrated over the range (- ∞,t), as occur in models of population growth. It is shown that Hopf bifurcation of periodic solutions from a steady state can occur, when a pair of eigenvalues crosses the imaginary axis. Also considered is the existence of traveling wave solutions of a model population equation allowing spatial diffusion in addition to the usual temporal variation. Lastly, the stability of the periodic solutions resulting from Hopf bifurcation is determined with aid of a Floquet theory.

The first chapter is devoted to linear integro-differential equations with constant coefficients utilizing the method of semi-groups of operators. The second chapter analyzes the Hopf bifurcation providing an existence theorem. Also, the two-timing perturbation procedure is applied to construct the periodic solutions. The third chapter uses two-timing to obtain traveling wave solutions of the diffusive model, as well as providing an existence theorem. The fourth chapter develops a Floquet theory for linear integro-differential equations with periodic coefficients again using the semi-group approach. The fifth chapter gives sufficient conditions for the stability or instability of a periodic solution in terms of the linearization of the equations. These results are then applied to the Hopf bifurcation problem and to a certain population equation modeling periodically fluctuating environments to deduce the stability of the corresponding periodic solutions.

Exact solutions and transformation properties of nonlinear partial differential equations from general relativity

Various families of exact solutions to the Einstein and Einstein-Maxwell field equations of General Relativity are treated for situations of sufficient symmetry that only two independent variables arise. The mathematical problem then reduces to consideration of sets of two coupled nonlinear differential equations.

The physical situations in which such equations arise include: a) the external gravitational field of an axisymmetric, uncharged steadily rotating body, b) cylindrical gravitational waves with two degrees of freedom, c) colliding plane gravitational waves, d) the external gravitational and electromagnetic fields of a static, charged axisymmetric body, and e) colliding plane electromagnetic and gravitational waves. Through the introduction of suitable potentials and coordinate transformations, a formalism is presented which treats all these problems simultaneously. These transformations and potentials may be used to generate new solutions to the Einstein-Maxwell equations from solutions to the vacuum Einstein equations, and vice-versa.

The calculus of differential forms is used as a tool for generation of similarity solutions and generalized similarity solutions. It is further used to find the invariance group of the equations; this in turn leads to various finite transformations that give new, physically distinct solutions from old. Some of the above results are then generalized to the case of three independent variables.

The stability of traveling wave solutions of parabolic equations

A method for determining by inspection the stability or instability of any solution u(t,x) = ɸ(x-ct) of any smooth equation of the form u_t = f(u_(xx),u_x,u where ∂/∂a f(a,b,c) > 0 for all arguments a,b,c, is developed. The connection between the mean wavespeed of solutions u(t,x) and their initial conditions u(0,x) is also explored. The mean wavespeed results and some of the stability results are then extended to include equations which contain integrals and also to include some special systems of equations. The results are applied to several physical examples.

Topics in vortex motion

Six topics in incompressible, inviscid fluid flow involving vortex motion are presented. The stability of the unsteady flow field due to the vortex filament expanding under the influence of an axial compression is examined in the first chapter as a possible model of the vortex bursting observed in aircraft contrails. The filament with a stagnant core is found to be unstable to axisymmetric disturbances. For initial disturbances with the form of axisymmetric Kelvin waves, the filament with a uniformly rotating core is neutrally stable, but the compression causes the disturbance to undergo a rapid increase in amplitude. The time at which the increase occurs is, however, later than the observed bursting times, indicating the bursting phenomenon is not caused by this type of instability.

In the second and third chapters the stability of a steady vortex filament deformed by two-dimensional strain and shear flows, respectively, is examined. The steady deformations are in the plane of the vortex cross-section. Disturbances which deform the filament centerline into a wave which does not propagate along the filament are shown to be unstable and a method is described to calculate the wave number and corresponding growth rate of the amplified waves for a general distribution of vorticity in the vortex core.

In Chapter Four exact solutions are constructed for two-dimensional potential flow over a wing with a free ideal vortex standing over the wing. The loci of positions of the free vortex are found and the lift is calculated. It is found that the lift on the wing can be significantly increased by the free vortex.

The two-dimensional trajectories of an ideal vortex pair near an orifice are calculated in Chapter Five. Three geometries are examined, and the criteria for the vortices to travel away from the orifice are determined.

Finally, Chapter Six reproduces completely the paper, "Structure of a linear array of hollow vortices of finite cross-section," co-authored with G. R. Baker and P. G. Saffman. Free streamline theory is employed to construct an exact steady solution for a linear array of hollow, or stagnant cored vortices. If each vortex has area A and the separation is L, then there are two possible shapes if A^(1/2)/L is less than 0.38 and none if it is larger. The stability of the shapes to two-dimensional, periodic and symmetric disturbances is considered for hollow vortices. The more deformed of the two possible shapes is found to be unstable, while the less deformed shape is stable.

Existence, uniqueness, and stability of solutions of a class of nonlinear partial differential equations

In this study we investigate the existence, uniqueness and asymptotic stability of solutions of a class of nonlinear integral equations which are representations for some time dependent non- linear partial differential equations. Sufficient conditions are established which allow one to infer the stability of the nonlinear equations from the stability of the linearized equations. Improved estimates of the domain of stability are obtained using a Liapunov Functional approach. These results are applied to some nonlinear partial differential equations governing the behavior of nonlinear continuous dynamical systems.

Nonexistence of looping trajectories in hydromagnetic waves of finite amplitude. Breaking of waves in a cold collision-free plasma in a magnetic field. On stabilities of periodic waves in a cold collision-free plasma in a magnetic field.

This dissertation consists of three parts. In Part I, it is shown that looping trajectories cannot exist in finite amplitude stationary hydromagnetic waves propagating across a magnetic field in a quasi-neutral cold collision-free plasma. In Part II, time-dependent solutions in series expansion are presented for the magnetic piston problem, which describes waves propagating into a quasi-neutral cold collision-free plasma, ensuing from magnetic disturbances on the boundary of the plasma. The expansion is equivalent to Picard's successive approximations. It is then shown that orbit crossings of plasma particles occur on the boundary for strong disturbances and inside the plasma for weak disturbances. In Part III, the existence of periodic waves propagating at an arbitrary angle to the magnetic field in a plasma is demonstrated by Stokes expansions in amplitude. Then stability analysis is made for such periodic waves with respect to side-band frequency disturbances. It is shown that waves of slow mode are unstable whereas waves of fast mode are stable if the frequency is below the cutoff frequency. The cutoff frequency depends on the propagation angle. For longitudinal propagation the cutoff frequency is equal to one-fourth of the electron's gyrofrequency. For transverse propagation the cutoff frequency is so high that waves of all frequencies are stable.

Non-linear dispersive waves with a small dissipation

The general theory of Whitham for slowly-varying non-linear wavetrains is extended to the case where some of the defining partial differential equations cannot be put into conservation form. Typical examples are considered in plasma dynamics and water waves in which the lack of a conservation form is due to dissipation; an additional non-conservative element, the presence of an external force, is treated for the plasma dynamics example. Certain numerical solutions of the water waves problem (the Korteweg-de Vries equation with dissipation) are considered and compared with perturbation expansions about the linearized solution; it is found that the first correction term in the perturbation expansion is an excellent qualitative indicator of the deviation of the dissipative decay rate from linearity.

A method for deriving necessary and sufficient conditions for the existence of a general uniform wavetrain solution is presented and illustrated in the plasma dynamics problem. Peaking of the plasma wave is demonstrated, and it is shown that the necessary and sufficient existence conditions are essentially equivalent to the statement that no wave may have an amplitude larger than the peaked wave.

A new type of fully non-linear stability criterion is developed for the plasma uniform wavetrain. It is shown explicitly that this wavetrain is stable in the near-linear limit. The nature of this new type of stability is discussed.

Steady shock solutions are also considered. By a quite general method, it is demonstrated that the plasma equations studied here have no steady shock solutions whatsoever. A special type of steady shock is proposed, in which a uniform wavetrain joins across a jump discontinuity to a constant state. Such shocks may indeed exist for the Korteweg-de Vries equation, but are barred from the plasma problem because entropy would decrease across the shock front.

Finally, a way of including the Landau damping mechanism in the plasma equations is given. It involves putting in a dissipation term of convolution integral form, and parallels a similar approach of Whitham in water wave theory. An important application of this would be towards resolving long-standing difficulties about the "collisionless" shock.

Some approximate solutions of dynamic problems in the linear theory of thin elastic shells

Some aspects of wave propagation in thin elastic shells are considered. The governing equations are derived by a method which makes their relationship to the exact equations of linear elasticity quite clear. Finite wave propagation speeds are ensured by the inclusion of the appropriate physical effects.

The problem of a constant pressure front moving with constant velocity along a semi-infinite circular cylindrical shell is studied. The behavior of the solution immediately under the leading wave is found, as well as the short time solution behind the characteristic wavefronts. The main long time disturbance is found to travel with the velocity of very long longitudinal waves in a bar and an expression for this part of the solution is given.

When a constant moment is applied to the lip of an open spherical shell, there is an interesting effect due to the focusing of the waves. This phenomenon is studied and an expression is derived for the wavefront behavior for the first passage of the leading wave and its first reflection.

For the two problems mentioned, the method used involves reducing the governing partial differential equations to ordinary differential equations by means of a Laplace transform in time. The information sought is then extracted by doing the appropriate asymptotic expansion with the Laplace variable as parameter.

Aqueous ring-opening metathesis polymerizations

Past workers in this group as well as in others have made considerable progress in the understanding and development of the ring-opening metathesis polymerization (ROMP) technique. Through these efforts, ROMP chemistry has become something of an organometallic success story. Extensive work was devoted to trying to identify the catalytically active species in classical reaction mixtures of early metal halides and alkyl aluminum compounds. Through this work, a mechanism involving the interconversion of metal carbenes and metallacyclobutanes was proposed. This preliminary work finally led to the isolation and characterization of stable metal carbene and metallacyclobutane complexes. As anticipated, these well-characterized complexes were shown to be active catalysts. In a select number of cases, these catalysts have been shown to catalyze the living polymerization of strained rings such as norbornene. The synthetic control offered by these living systems places them in a unique category of metal catalyzed reactions. To take full advantage of these new catalysts, two approaches should be explored. The first takes advantage of the unusual fact that all of the unsaturation present in the monomer is conserved in the polymer product. This makes ROMP techniques ideal for the synthesis of highly unsaturated, and fully conjugated polymers, which find uses in a variety of applications. This area is currently under intense investigation. The second aspect, which should lend itself to fruitful investigations, is expanding the utility of these catalysts through the living polymerization of monomers containing interesting functional groups. Polymer properties can be dramatically altered by the incorporation of functional groups. It is this latter aspect which will be addressed in this work.

After a general introduction to both the ring-opening metathesis reaction (Chapter 1) and the polymerization of fuctionalized monomers by transition metal catalysts (Chapter 2), the limits of the existing living ROMP catalysts with functionalized monomers are examined in Chapter 3. Because of the stringent limitations of these early metal catalysts, efforts were focused on catalysts based on ruthenium complexes. Although not living, and displaying unusually long induction periods, these catalysts show high promise for future investigations directed at the development of catalysts for the living polymerization of functionalized monomers. In an attempt to develop useful catalysts based on these ruthenium complexes, efforts to increase their initiation rates are presented in Chapter 4. This work eventually led to the discovery that these catalysts are highly active in aqueous solution, providing the opportunity to develop aqueous emulsion ROMP systems. Recycling the aqueous catalysts led to the discovery that the ruthenium complexes become more activated with use. Investigations of these recycled solutions uncovered new ruthenium-olefin complexes, which are implicated in the activation process. Although our original goal of developing living ROMP catalysts for the polymerization of fuctionalized monomers is yet to be realized, it is hoped that this work provides a foundation from which future investigations can be launched.

In the last chapter, the ionophoric properties of the poly(7-oxanobornene) materials is briefly discussed. Their limited use as acyclic host polymers led to investigations into the fabrication of ion-permeable membranes fashioned from these materials.

Sustainable energy solutions for irrigation and harvesting in developing countries

One of the critical problems currently being faced by agriculture industry in developing nations is the alarming rate of groundwater depletion. Irrigation accounts for over 70% of the total groundwater withdrawn everyday. Compounding this issue is the use of polluting diesel generators to pump groundwater for irrigation. This has made irrigation not only the biggest consumer of groundwater but also one of the major contributors to green house gases. The aim of this thesis is to present a solution to the energy-water nexus. To make agriculture less dependent on fossil fuels, the use of a solar-powered Stirling engine as the power generator for on-farm energy needs is discussed. The Stirling cycle is revisited and practical and ideal Stirling cycles are compared. Based on agricultural needs and financial constraints faced by farmers in developing countries, the use of a Fresnel lens as a solar-concentrator and a Beta-type Stirling engine unit is suggested for sustainable power generation on the farms. To reduce the groundwater consumption and to make irrigation more sustainable, the conceptual idea of using a Stirling engine in drip irrigation is presented. To tackle the shortage of over 37 million tonnes of cold-storage in India, the idea of cost-effective solar-powered on-farm cold storage unit is discussed.

Investigations of charge-carrier dynamics at semiconductor/liquid interfaces

Theoretical and experimental investigations of charge-carrier dynamics at semiconductor/liquid interfaces, specifically with respect to interfacial electron transfer and surface recombination, are presented.

Fermi's golden rule has been used to formulate rate expressions for charge transfer of delocalized carriers in a nondegenerately doped semiconducting electrode to localized, outer-sphere redox acceptors in an electrolyte phase. The treatment allows comparison between charge-transfer kinetic data at metallic, semimetallic, and semiconducting electrodes in terms of parameters such as the electronic coupling to the electrode, the attenuation of coupling with distance into the electrolyte, and the reorganization energy of the charge-transfer event. Within this framework, rate constant values expected at representative semiconducting electrodes have been determined from experimental data for charge transfer at metallic electrodes. The maximum rate constant (i.e., at optimal exoergicity) for outer-sphere processes at semiconducting electrodes is computed to be in the range 10^-17-10^-16 cm⁴ s^-1, which is in excellent agreement with prior theoretical models and experimental results for charge-transfer kinetics at semiconductor/liquid interfaces.

Double-layer corrections have been evaluated for semiconductor electrodes in both depletion and accumulation conditions. In conjuction with the Gouy-Chapman-Stern model, a finite difference approach has been used to calculate potential drops at a representative solid/liquid interface. Under all conditions that were simulated, the correction to the driving force used to evaluate the interfacial rate constant was determined to be less than 2% of the uncorrected interfacial rate constant.

Photoconductivity decay lifetimes have been obtained for Si(111) in contact with solutions of CH₃OH or tetrahydrofuran containing one-electron oxidants. Silicon surfaces in contact with electrolyte solutions having Nernstian redox potentials > 0 V vs. SCE exhibited low effective surface recombination velocities regardless of the different surface chemistries. The formation of an inversion layer, and not a reduced density of electrical trap sites on the surface, is shown to be responsible for the long charge-carrier lifetimes observed for these systems. In addition, a method for preparing an air-stable, low surface recombination velocity Si surface through a two-step, chlorination/alkylation reaction is described.

Cooperative and market-based solutions to pollution abatement problems

This work concerns itself with the possibility of solutions, both cooperative and market based, to pollution abatement problems. In particular, we are interested in pollutant emissions in Southern California and possible solutions to the abatement problems enumerated in the 1990 Clean Air Act. A tradable pollution permit program has been implemented to reduce emissions, creating property rights associated with various pollutants.

Before we discuss the performance of market-based solutions to LA's pollution woes, we consider the existence of cooperative solutions. In Chapter 2, we examine pollutant emissions as a trans boundary public bad. We show that for a class of environments in which pollution moves in a bi-directional, acyclic manner, there exists a sustainable coalition structure and associated levels of emissions. We do so via a new core concept, one more appropriate to modeling cooperative emissions agreements (and potential defection from them) than the standard definitions.

However, this leaves the question of implementing pollution abatement programs unanswered. While the existence of a cost-effective permit market equilibrium has long been understood, the implementation of such programs has been difficult. The design of Los Angeles' REgional CLean Air Incentives Market (RECLAIM) alleviated some of the implementation problems, and in part exacerbated them. For example, it created two overlapping cycles of permits and two zones of permits for different geographic regions. While these design features create a market that allows some measure of regulatory control, they establish a very difficult trading environment with the potential for inefficiency arising from the transactions costs enumerated above and the illiquidity induced by the myriad assets and relatively few participants in this market.

It was with these concerns in mind that the ACE market (Automated Credit Exchange) was designed. The ACE market utilizes an iterated combined-value call market (CV Market). Before discussing the performance of the RECLAIM program in general and the ACE mechanism in particular, we test experimentally whether a portfolio trading mechanism can overcome market illiquidity. Chapter 3 experimentally demonstrates the ability of a portfolio trading mechanism to overcome portfolio rebalancing problems, thereby inducing sufficient liquidity for markets to fully equilibrate.

With experimental evidence in hand, we consider the CV Market's performance in the real world. We find that as the allocation of permits reduces to the level of historical emissions, prices are increasing. As of April of this year, prices are roughly equal to the cost of the Best Available Control Technology (BACT). This took longer than expected, due both to tendencies to mis-report emissions under the old regime, and abatement technology advances encouraged by the program. Vve also find that the ACE market provides liquidity where needed to encourage long-term planning on behalf of polluting facilities.

Adsorption of Pb(II) and Cu(II) on α-quartz from aqueous solutions: influence of pH, ionic strength, and complexing ligands

Adsorption of aqueous Pb(II) and Cu(II) on α-quartz was studied as a function of time, system surface area, and chemical speciation. Experimental systems contained sodium as a major cation, hydroxide, carbonate, and chloride as major anions, and covered the pH range 4 to 8. In some cases citrate and EDTA were added as representative organic complexing agents. The adsorption equilibria were reached quickly, regardless of the system surface area. The positions of the adsorption equilibria were found to be strongly dependent on pH, ionic strength and concentration of citrate and EDTA. The addition of these non-adsorbing ligands resulted in a competition between chelation and adsorption. The experimental work also included the examination of the adsorption behavior of the doubly charged major cations Ca(II) and Mg(II) as a function of pH.

The theoretical description of the experimental systems was obtained by means of chemical equilibrium-plus-adsorption computations using two adsorption models: one mainly electrostatic (the James-Healy Model), and the other mainly chemical (the Ion Exchange-Surface Complex Formation Model). Comparisons were made between these two models.

The main difficulty in the theoretical predictions of the adsorption behavior of Cu(II) was the lack of the reliable data for the second hydrolysis constant(*β_2) The choice of the constant was made on the basis of potentiometric titratlons of Cu^(2+)

The experimental data obtained and the resulting theoretical observations were applied in models of the chemical behavior of trace metals in fresh oxic waters, with emphasis on Pb(II) and Cu(II).

Theoretical and experimental investigations of the flocculation of charged particles in aqueous solutions by polyelectrolytes of opposite charge

An electrostatic mechanism for the flocculation of charged particles by polyelectrolytes of opposite charge is proposed. The difference between this and previous electrostatic coagulation mechanisms is the formation of charged polyion patches on the oppositely charged surfaces. The size of a patch is primarily a function of polymer molecular weight and the total patch area is a function of the amount of polymer adsorbed. The theoretical predictions of the model agree with the experimental dependence of the polymer dose required for flocculation on polymer molecular weight and solution ionic strength.

A theoretical analysis based on the Derjaguin-Landau, Verwey- Overbeek electrical double layer theory and statistical mechanical treatments of adsorbed polymer configurations indicates that flocculation of charged particles in aqueous solutions by polyelectrolytes of opposite charge does not occur by the commonly accepted polymerbridge mechanism.

A series of 1, 2-dimethyl-5 -vinylpyridinium bromide polymers with a molecular weight range of 6x10^3 to 5x10^6 was synthesized and used to flocculate dilute polystyrene latex and silica suspensions in solutions of various ionic strengths. It was found that with high molecular weight polymers and/or high ionic strengths the polymer dose required for flocculation is independent of molecular weight. With low molecular weights and/or low ionic strengths, the flocculation dose decreases with increasing molecular weight.