16 resultados para Combustion, Theory of.

em CaltechTHESIS


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In Part I the kinetic theory of excitations in flowing liquid He II is developed to a higher order than that carried out previously, by Landau and Khalatnikov, in order to demonstrate the existence of non-equilibrium terms of a new nature in the hydrodynamic equations. It is then shown that these terms can lead to spontaneous destabilization in counter currents when the relative velocity of the normal and super fluids exceeds a critical value that depends on the temperature, but not on geometry. There are no adjustable parameters in the theory. The critical velocities are estimated to be in the 14-20 m/sec range for T ≤ 2.0° K, but tend to zero as T → T_λ. The possibility that these critical velocities may be related to the experimentally observed "intrinsic" critical velocities is discussed.

Part II consists of a semi-classical investigation of rotonquantized vortex line interactions. An essentially classical model is used for the collision and the behavior of the roton in the vortex field is investigated in detail. From this model it is possible to derive the HVBK mutual friction terms that appear in the phenomenalogical equations of motion for rotating liquid He II. Estimates of the Hall and Vinen B and B' coefficients are in good agreement with experiments. The claim is made that the theory does not contain any arbitrary adjustable parameters.

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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.

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The theory of bifurcation of solutions to two-point boundary value problems is developed for a system of nonlinear first order ordinary differential equations in which the bifurcation parameter is allowed to appear nonlinearly. An iteration method is used to establish necessary and sufficient conditions for bifurcation and to construct a unique bifurcated branch in a neighborhood of a bifurcation point which is a simple eigenvalue of the linearized problem. The problem of bifurcation at a degenerate eigenvalue of the linearized problem is reduced to that of solving a system of algebraic equations. Cases with no bifurcation and with multiple bifurcation at a degenerate eigenvalue are considered.

The iteration method employed is shown to generate approximate solutions which contain those obtained by formal perturbation theory. Thus the formal perturbation solutions are rigorously justified. A theory of continuation of a solution branch out of the neighborhood of its bifurcation point is presented. Several generalizations and extensions of the theory to other types of problems, such as systems of partial differential equations, are described.

The theory is applied to the problem of the axisymmetric buckling of thin spherical shells. Results are obtained which confirm recent numerical computations.

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The primary focus of this thesis is on the interplay of descriptive set theory and the ergodic theory of group actions. This incorporates the study of turbulence and Borel reducibility on the one hand, and the theory of orbit equivalence and weak equivalence on the other. Chapter 2 is joint work with Clinton Conley and Alexander Kechris; we study measurable graph combinatorial invariants of group actions and employ the ultraproduct construction as a way of constructing various measure preserving actions with desirable properties. Chapter 3 is joint work with Lewis Bowen; we study the property MD of residually finite groups, and we prove a conjecture of Kechris by showing that under general hypotheses property MD is inherited by a group from one of its co-amenable subgroups. Chapter 4 is a study of weak equivalence. One of the main results answers a question of Abért and Elek by showing that within any free weak equivalence class the isomorphism relation does not admit classification by countable structures. The proof relies on affirming a conjecture of Ioana by showing that the product of a free action with a Bernoulli shift is weakly equivalent to the original action. Chapter 5 studies the relationship between mixing and freeness properties of measure preserving actions. Chapter 6 studies how approximation properties of ergodic actions and unitary representations are reflected group theoretically and also operator algebraically via a group's reduced C*-algebra. Chapter 7 is an appendix which includes various results on mixing via filters and on Gaussian actions.

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Three separate topics, each stimulated by experiments, are treated theoretically in this dessertation: isotopic effects of ozone, electron transfer at interfaces, and intramolecular directional electron transfer in a supramolecular system.

The strange mass-independent isotope effect for the enrichment of ozone, which has been a puzzle in the literature for some 20 years, and the equally puzzling unconventional strong mass-dependent effect of individual reaction rate constants are studied as different aspects of a symmetry-driven behavior. A statistical (RRKM-based) theory with a hindered-rotor transition state is used. The individual rate constant ratios of recombination reactions at low pressures are calculated using the theory involving (1) small deviation from the statistical density of states for symmetric isotopomers, and (2) weak collisions for deactivation of the vibrationally excited ozone molecules. The weak collision and partitioning among exit channels play major roles in producing the large unconventional isotope effect in "unscrambled" systems. The enrichment studies reflect instead the non-statistical effect in "scrambled" systems. The theoretical results of low-pressure ozone enrichments and individual rate constant ratios obtained from these calculations are consistent with the corresponding experimental results. The isotopic exchange rate constant for the reaction ^(16)O + ^(18)O ^(18)O→+ ^(16)O ^(18)O + ^(18)O provides information on the nature of a variationally determined hindered-rotor transition state using experimental data at 130 K and 300 K. Pressure effects on the recombination rate constant, on the individual rate constant ratios and on the enrichments are also investigated. The theoretical results are consistent with the experimental data. The temperature dependence of the enrichment and rate constant ratios is also discussed, and experimental tests are suggested. The desirability of a more accurate potential energy surface for ozone in the transition state region is also noted.

Electron transfer reactions at semiconductor /liquid interfaces are studied using a tight-binding model for the semiconductors. The slab method and a z-transform method are employed in obtaining the tight-binding electronic structures of semiconductors having surfaces. The maximum electron transfer rate constants at Si/viologen^(2-/+) and InP /Me_(2)Fc^(+/O) interfaces are computed using the tight-binding type calculations for the solid and the extended-Huckel for the coupling to the redox agent at the interface. These electron transfer reactions are also studied using a free electron model for the semiconductor and the redox molecule, where Bardeen's method is adapted to calculate the coupling matrix element between the molecular and semiconductor electronic states. The calculated results for maximum rate constant of the electron transfer from the semiconductor bulk states are compared with the experimentally measured values of Lewis and coworkers, and are in reasonable agreement, without adjusting parameters. In the case of InP /liquid interface, the unusual current vs applied potential behavior is additionally interpreted, in part, by the presence of surface states.

Photoinduced electron transfer reactions in small supramolecular systems, such as 4-aminonaphthalimide compounds, are interesting in that there are, in principle, two alternative pathways (directions) for the electron transfer. The electron transfer, however, is unidirectional, as deduced from pH-dependent fluorescence quenching studies on different compounds. The role of electronic coupling matrix element and the charges in protonation are considered to explain the directionality of the electron transfer and other various results. A related mechanism is proposed to interpret the fluorescence behavior of similar molecules as fluorescent sensors of metal ions.

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The rate of electron transport between distant sites was studied. The rate depends crucially on the chemical details of the donor, acceptor, and surrounding medium. These reactions involve electron tunneling through the intervening medium and are, therefore, profoundly influenced by the geometry and energetics of the intervening molecules. The dependence of rate on distance was considered for several rigid donor-acceptor "linkers" of experimental importance. Interpretation of existing experiments and predictions for new experiments were made.

The electronic and nuclear motion in molecules is correlated. A Born-Oppenheimer separation is usually employed in quantum chemistry to separate this motion. Long distance electron transfer rate calculations require the total donor wave function when the electron is very far from its binding nuclei. The Born-Oppenheimer wave functions at large electronic distance are shown to be qualitatively wrong. A model which correctly treats the coupling was proposed. The distance and energy dependence of the electron transfer rate was determined for such a model.

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Close to equilibrium, a normal Bose or Fermi fluid can be described by an exact kinetic equation whose kernel is nonlocal in space and time. The general expression derived for the kernel is evaluated to second order in the interparticle potential. The result is a wavevector- and frequency-dependent generalization of the linear Uehling-Uhlenbeck kernel with the Born approximation cross section.

The theory is formulated in terms of second-quantized phase space operators whose equilibrium averages are the n-particle Wigner distribution functions. Convenient expressions for the commutators and anticommutators of the phase space operators are obtained. The two-particle equilibrium distribution function is analyzed in terms of momentum-dependent quantum generalizations of the classical pair distribution function h(k) and direct correlation function c(k). The kinetic equation is presented as the equation of motion of a two -particle correlation function, the phase space density-density anticommutator, and is derived by a formal closure of the quantum BBGKY hierarchy. An alternative derivation using a projection operator is also given. It is shown that the method used for approximating the kernel by a second order expansion preserves all the sum rules to the same order, and that the second-order kernel satisfies the appropriate positivity and symmetry conditions.

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The problem of s-d exchange scattering of conduction electrons off localized magnetic moments in dilute magnetic alloys is considered employing formal methods of quantum field theoretical scattering. It is shown that such a treatment not only allows for the first time, the inclusion of multiparticle intermediate states in single particle scattering equations but also results in extremely simple and straight forward mathematical analysis. These equations are proved to be exact in the thermodynamic limit. A self-consistent integral equation for electron self energy is derived and approximately solved. The ground state and physical parameters of dilute magnetic alloys are discussed in terms of the theoretical results. Within the approximation of single particle intermediate states our results reduce to earlier versions. The following additional features are found as a consequence of the inclusion of multiparticle intermediate states;

(i) A non analytic binding energy is pre sent for both, antiferromagnetic (J < o) and ferromagnetic (J > o) couplings of the electron plus impurity system.

(ii) The correct behavior of the energy difference of the conduction electron plus impurity system and the free electron system is found which is free of unphysical singularities present in earlier versions of the theories.

(iii) The ground state of the conduction electron plus impurity system is shown to be a many-body condensate state for J < o and J > o, both. However, a distinction is made between the usual terminology of "Singlet" and "Triplet" ground states and nature of our ground state.

(iv) It is shown that a long range ordering, leading to an ordering of the magnetic moments can result from a contact interaction such as the s-d exchange interaction.

(v) The explicit dependence of the excess specific heat of the Kondo systems is obtained and found to be linear in temperatures as T→ o and T ℓnT for 0.3 T_K ≤ T ≤ 0.6 T_K. A rise in (ΔC/T) for temperatures in the region 0 < T ≤ 0.1 T_K is predicted. These results are found to be in excellent agreement with experiments.

(vi) The existence of a critical temperature for Ferromagnetic coupling (J > o) is shown. On the basis of this the apparent contradiction of the simultaneous existence of giant moments and Kondo effect is resolved.

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The problem is to calculate the attenuation of plane sound waves passing through a viscous, heat-conducting fluid containing small spherical inhomogeneities. The attenuation is calculated by evaluating the rate of increase of entropy caused by two irreversible processes: (1) the mechanical work done by the viscous stresses in the presence of velocity gradients, and (2) the flow of heat down the thermal gradients. The method is first applied to a homogeneous fluid with no spheres and shown to give the classical Stokes-Kirchhoff expressions. The method is then used to calculate the additional viscous and thermal attenuation when small spheres are present. The viscous attenuation agrees with Epstein's result obtained in 1941 for a non-heat-conducting fluid. The thermal attenuation is found to be similar in form to the viscous attenuation and, for gases, of comparable magnitude. The general results are applied to the case of water drops in air and air bubbles in water.

For water drops in air the viscous and thermal attenuations are camparable; the thermal losses occur almost entirely in the air, the thermal dissipation in the water being negligible. The theoretical values are compared with Knudsen's experimental data for fogs and found to agree in order of magnitude and dependence on frequency. For air bubbles in water the viscous losses are negligible and the calculated attenuation is almost completely due to thermal losses occurring in the air inside the bubbles, the thermal dissipation in the water being relatively small. (These results apply only to non-resonant bubbles whose radius changes but slightly during the acoustic cycle.)

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In Part I, we construct a symmetric stress-energy-momentum pseudo-tensor for the gravitational fields of Brans-Dicke theory, and use this to establish rigorously conserved integral expressions for energy-momentum Pi and angular momentum Jik. Application of the two-dimensional surface integrals to the exact static spherical vacuum solution of Brans leads to an identification of our conserved mass with the active gravitational mass. Application to the distant fields of an arbitrary stationary source reveals that Pi and Jik have the same physical interpretation as in general relativity. For gravitational waves whose wavelength is small on the scale of the background radius of curvature, averaging over several wavelengths in the Brill-Hartle-Isaacson manner produces a stress-energy-momentum tensor for gravitational radiation which may be used to calculate the changes in Pi and Jik of their source.

In Part II, we develop strong evidence in favor of a conjecture by Penrose--that, in the Brans-Dicke theory, relativistic gravitational collapse in three dimensions produce black holes identical to those of general relativity. After pointing out that any black hole solution of general relativity also satisfies Brans-Dicke theory, we establish the Schwarzschild and Kerr geometries as the only possible spherical and axially symmetric black hole exteriors, respectively. Also, we show that a Schwarzschild geometry is necessarily formed in the collapse of an uncharged sphere.

Appendices discuss relationships among relativistic gravity theories and an example of a theory in which black holes do not exist.

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An attempt is made to provide a theoretical explanation of the effect of the positive column on the voltage-current characteristic of a glow or an arc discharge. Such theories have been developed before, and all are based on balancing the production and loss of charged particles and accounting for the energy supplied to the plasma by the applied electric field. Differences among the theories arise from the approximations and omissions made in selecting processes that affect the particle and energy balances. This work is primarily concerned with the deviation from the ambipolar description of the positive column caused by space charge, electron-ion volume recombination, and temperature inhomogeneities.

The presentation is divided into three parts, the first of which involved the derivation of the final macroscopic equations from kinetic theory. The final equations are obtained by taking the first three moments of the Boltzmann equation for each of the three species in the plasma. Although the method used and the equations obtained are not novel, the derivation is carried out in detail in order to appraise the validity of numerous approximations and to justify the use of data from other sources. The equations are applied to a molecular hydrogen discharge contained between parallel walls. The applied electric field is parallel to the walls, and the dependent variables—electron and ion flux to the walls, electron and ion densities, transverse electric field, and gas temperature—vary only in the direction perpendicular to the walls. The mathematical description is given by a sixth-order nonlinear two-point boundary value problem which contains the applied field as a parameter. The amount of neutral gas and its temperature at the walls are held fixed, and the relation between the applied field and the electron density at the center of the discharge is obtained in the process of solving the problem. This relation corresponds to that between current and voltage and is used to interpret the effect of space charge, recombination, and temperature inhomogeneities on the voltage-current characteristic of the discharge.

The complete solution of the equations is impractical both numerically and analytically, and in Part II the gas temperature is assumed uniform so as to focus on the combined effects of space charge and recombination. The terms representing these effects are treated as perturbations to equations that would otherwise describe the ambipolar situation. However, the term representing space charge is not negligible in a thin boundary layer or sheath near the walls, and consequently the perturbation problem is singular. Separate solutions must be obtained in the sheath and in the main region of the discharge, and the relation between the electron density and the applied field is not determined until these solutions are matched.

In Part III the electron and ion densities are assumed equal, and the complicated space-charge calculation is thereby replaced by the ambipolar description. Recombination and temperature inhomogeneities are both important at high values of the electron density. However, the formulation of the problem permits a comparison of the relative effects, and temperature inhomogeneities are shown to be important at lower values of the electron density than recombination. The equations are solved by a direct numerical integration and by treating the term representing temperature inhomogeneities as a perturbation.

The conclusions reached in the study are primarily concerned with the association of the relation between electron density and axial field with the voltage-current characteristic. It is known that the effect of space charge can account for the subnormal glow discharge and that the normal glow corresponds to a close approach to an ambipolar situation. The effect of temperature inhomogeneities helps explain the decreasing characteristic of the arc, and the effect of recombination is not expected to appear except at very high electron densities.

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Interest in the possible applications of a priori inequalities in linear elasticity theory motivated the present investigation. Korn's inequality under various side conditions is considered, with emphasis on the Korn's constant. In the "second case" of Korn's inequality, a variational approach leads to an eigenvalue problem; it is shown that, for simply-connected two-dimensional regions, the problem of determining the spectrum of this eigenvalue problem is equivalent to finding the values of Poisson's ratio for which the displacement boundary-value problem of linear homogeneous isotropic elastostatics has a non-unique solution.

Previous work on the uniqueness and non-uniqueness issue for the latter problem is examined and the results applied to the spectrum of the Korn eigenvalue problem. In this way, further information on the Korn constant for general regions is obtained.

A generalization of the "main case" of Korn's inequality is introduced and the associated eigenvalue problem is a gain related to the displacement boundary-value problem of linear elastostatics in two dimensions.

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The problem of the continuation to complex values of the angular momentum of the partial wave amplitude is examined for the simplest production process, that of two particles → three particles. The presence of so-called "anomalous singularities" complicates the procedure followed relative to that used for quasi two-body scattering amplitudes. The anomalous singularities are shown to lead to exchange degenerate amplitudes with possible poles in much the same way as "normal" singularities lead to the usual signatured amplitudes. The resulting exchange-degenerate trajectories would also be expected to occur in two-body amplitudes.

The representation of the production amplitude in terms of the singularities of the partial wave amplitude is then developed and applied to the high energy region, with attention being paid to the emergence of "double Regge" terms. Certain new results are obtained for the behavior of the amplitude at zero momentum transfer, and some predictions of polarization and minima in momentum transfer distributions are made. A calculation of the polarization of the ρo meson in the reaction π - p → π - ρop at high energy with small momentum transfer to the proton is compared with data taken at 25 Gev by W. D. Walker and collaborators. The result is favorable, although limited by the statistics of the available data.

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An equation for the reflection which results when an expanding dielectric slab scatters normally incident plane electromagnetic waves is derived using the invariant imbedding concept. The equation is solved approximately and the character of the solution is investigated. Also, an equation for the radiation transmitted through such a slab is similarly obtained. An alternative formulation of the slab problem is presented which is applicable to the analogous problem in spherical geometry. The form of an equation for the modal reflections from a nonrelativistically expanding sphere is obtained and some salient features of the solution are described. In all cases the material is assumed to be a nondispersive, nonmagnetic dielectric whose rest frame properties are slowly varying.

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The propagation of waves in an extended, irregular medium is studied under the "quasi-optics" and the "Markov random process" approximations. Under these assumptions, a Fokker-Planck equation satisfied by the characteristic functional of the random wave field is derived. A complete set of the moment equations with different transverse coordinates and different wavenumbers is then obtained from the characteristic functional. The derivation does not require Gaussian statistics of the random medium and the result can be applied to the time-dependent problem. We then solve the moment equations for the phase correlation function, angular broadening, temporal pulse smearing, intensity correlation function, and the probability distribution of the random waves. The necessary and sufficient conditions for strong scintillation are also given.

We also consider the problem of diffraction of waves by a random, phase-changing screen. The intensity correlation function is solved in the whole Fresnel diffraction region and the temporal pulse broadening function is derived rigorously from the wave equation.

The method of smooth perturbations is applied to interplanetary scintillations. We formulate and calculate the effects of the solar-wind velocity fluctuations on the observed intensity power spectrum and on the ratio of the observed "pattern" velocity and the true velocity of the solar wind in the three-dimensional spherical model. The r.m.s. solar-wind velocity fluctuations are found to be ~200 km/sec in the region about 20 solar radii from the Sun.

We then interpret the observed interstellar scintillation data using the theories derived under the Markov approximation, which are also valid for the strong scintillation. We find that the Kolmogorov power-law spectrum with an outer scale of 10 to 100 pc fits the scintillation data and that the ambient averaged electron density in the interstellar medium is about 0.025 cm-3. It is also found that there exists a region of strong electron density fluctuation with thickness ~10 pc and mean electron density ~7 cm-3 between the PSR 0833-45 pulsar and the earth.