Part I. Influence of membrane morphology on ion-exchange and charge propagation in composite polyelectrolyte electrode coatings. Part II. Dynamic surface tension measurements of polarization relaxation at mercury pool electrodes by the method of Wilhelmy.

Part I. Novel composite polyelectrolyte materials were developed that exhibit desirable charge propagation and ion-retention properties. The morphology of electrode coatings cast from these materials was shown to be more important for its electrochemical behavior than its chemical composition.

Part II. The Wilhelmy plate technique for measuring dynamic surface tension was extended to electrified liquid-liquid interphases. The dynamical response of the aqueous NaF-mercury electrified interphase was examined by concomitant measurement of surface tension, current, and applied electrostatic potential. Observations of the surface tension response to linear sweep voltammetry and to step function perturbations in the applied electrostatic potential (e.g., chronotensiometry) provided strong evidence that relaxation processes proceed for time-periods that are at least an order of magnitude longer than the time periods necessary to establish diffusion equilibrium. The dynamical response of the surface tension is analyzed within the context of non-equilibrium thermodynamics and a kinetic model that requires three simultaneous first order processes.

Existence of the transverse relaxation time in optically excited bulk semiconductors

Two basic types of depolarization mechanisms, carrier-carrier (CC) and carrier-phonon (CP) scattering, are investigated in optically excited bulk semiconductors (3D), in which the existence of the transverse relaxation time is proven based on the vector property of the interband transition matrix elements. The dephasing rates for both CC and CP scattering are determined to be equal to one half of the total scattering-rate-integrals weighted by the factors (1 - cos chi), where chi are the scattering angles. Analytical expressions of the polarization dephasing due to CC scattering are established by using an uncertainty broadening approach, and analytical ones due to both the polar optical-phonon and non-polar deformation potential scattering (including inter-valley scattering) are also presented by using the sharp spectral functions in the dephasing rate calculations. These formulas, which reveal the trivial role of the Coulomb screening effect in the depolarization processes, are used to explain the experimental results at hand and provide a clear physical picture that is difficult to extract from numerical treatments.

Convex Relaxation for Low-Dimensional Representation: Phase Transitions and Limitations

There is a growing interest in taking advantage of possible patterns and structures in data so as to extract the desired information and overcome the curse of dimensionality. In a wide range of applications, including computer vision, machine learning, medical imaging, and social networks, the signal that gives rise to the observations can be modeled to be approximately sparse and exploiting this fact can be very beneficial. This has led to an immense interest in the problem of efficiently reconstructing a sparse signal from limited linear observations. More recently, low-rank approximation techniques have become prominent tools to approach problems arising in machine learning, system identification and quantum tomography.

In sparse and low-rank estimation problems, the challenge is the inherent intractability of the objective function, and one needs efficient methods to capture the low-dimensionality of these models. Convex optimization is often a promising tool to attack such problems. An intractable problem with a combinatorial objective can often be "relaxed" to obtain a tractable but almost as powerful convex optimization problem. This dissertation studies convex optimization techniques that can take advantage of low-dimensional representations of the underlying high-dimensional data. We provide provable guarantees that ensure that the proposed algorithms will succeed under reasonable conditions, and answer questions of the following flavor:

More specifically, i) Focusing on linear inverse problems, we generalize the classical error bounds known for the least-squares technique to the lasso formulation, which incorporates the signal model. ii) We show that intuitive convex approaches do not perform as well as expected when it comes to signals that have multiple low-dimensional structures simultaneously. iii) Finally, we propose convex relaxations for the graph clustering problem and give sharp performance guarantees for a family of graphs arising from the so-called stochastic block model. We pay particular attention to the following aspects. For i) and ii), we aim to provide a general geometric framework, in which the results on sparse and low-rank estimation can be obtained as special cases. For i) and iii), we investigate the precise performance characterization, which yields the right constants in our bounds and the true dependence between the problem parameters.

The origin of the transverse relaxation time in optically excited semiconductor quantum wells

The origin of the transverse relaxation time in optically excited semiconductor quantum wells is investigated based on the vector property of the interband transition matrix elements. The dephasing rate due to carrier-carrier (CC) scattering is found to be equal to half of the common momentum relaxation rate. The analytical expression of the polarization dephasing due to CC scattering in two-dimension is established and the dependence of the dephasing rate Gamma(cc) on the carrier density N is determined to be Gamma(cc) = constant (.) N-1/2, which is used to explain the experimental results and provides a promising physical picture. (C) 2004 Elsevier B.V. All rights reserved.

First principles based multiparadigm modeling of electronic structures and dynamics

Electronic structures and dynamics are the key to linking the material composition and structure to functionality and performance.

An essential issue in developing semiconductor devices for photovoltaics is to design materials with optimal band gaps and relative positioning of band levels. Approximate DFT methods have been justified to predict band gaps from KS/GKS eigenvalues, but the accuracy is decisively dependent on the choice of XC functionals. We show here for CuInSe₂ and CuGaSe₂, the parent compounds of the promising CIGS solar cells, conventional LDA and GGA obtain gaps of 0.0-0.01 and 0.02-0.24 eV (versus experimental values of 1.04 and 1.67 eV), while the historically first global hybrid functional, B3PW91, is surprisingly the best, with band gaps of 1.07 and 1.58 eV. Furthermore, we show that for 27 related binary and ternary semiconductors, B3PW91 predicts gaps with a MAD of only 0.09 eV, which is substantially better than all modern hybrid functionals, including B3LYP (MAD of 0.19 eV) and screened hybrid functional HSE06 (MAD of 0.18 eV).

The laboratory performance of CIGS solar cells (> 20% efficiency) makes them promising candidate photovoltaic devices. However, there remains little understanding of how defects at the CIGS/CdS interface affect the band offsets and interfacial energies, and hence the performance of manufactured devices. To determine these relationships, we use the B3PW91 hybrid functional of DFT with the AEP method that we validate to provide very accurate descriptions of both band gaps and band offsets. This confirms the weak dependence of band offsets on surface orientation observed experimentally. We predict that the CBO of perfect CuInSe₂/CdS interface is large, 0.79 eV, which would dramatically degrade performance. Moreover we show that band gap widening induced by Ga adjusts only the VBO, and we find that Cd impurities do not significantly affect the CBO. Thus we show that Cu vacancies at the interface play the key role in enabling the tunability of CBO. We predict that Na further improves the CBO through electrostatically elevating the valence levels to decrease the CBO, explaining the observed essential role of Na for high performance. Moreover we find that K leads to a dramatic decrease in the CBO to 0.05 eV, much better than Na. We suggest that the efficiency of CIGS devices might be improved substantially by tuning the ratio of Na to K, with the improved phase stability of Na balancing phase instability from K. All these defects reduce interfacial stability slightly, but not significantly.

A number of exotic structures have been formed through high pressure chemistry, but applications have been hindered by difficulties in recovering the high pressure phase to ambient conditions (i.e., one atmosphere and room temperature). Here we use dispersion-corrected DFT (PBE-ulg flavor) to predict that above 60 GPa the most stable form of N₂O (the laughing gas in its molecular form) is a 1D polymer with an all-nitrogen backbone analogous to cis-polyacetylene in which alternate N are bonded (ionic covalent) to O. The analogous trans-polymer is only 0.03-0.10 eV/molecular unit less stable. Upon relaxation to ambient conditions both polymers relax below 14 GPa to the same stable non-planar trans-polymer, accompanied by possible electronic structure transitions. The predicted phonon spectrum and dissociation kinetics validate the stability of this trans-poly-NNO at ambient conditions, which has potential applications as a new type of conducting polymer with all-nitrogen chains and as a high-energy oxidizer for rocket propulsion. This work illustrates in silico materials discovery particularly in the realm of extreme conditions.

Modeling non-adiabatic electron dynamics has been a long-standing challenge for computational chemistry and materials science, and the eFF method presents a cost-efficient alternative. However, due to the deficiency of FSG representation, eFF is limited to low-Z elements with electrons of predominant s-character. To overcome this, we introduce a formal set of ECP extensions that enable accurate description of p-block elements. The extensions consist of a model representing the core electrons with the nucleus as a single pseudo particle represented by FSG, interacting with valence electrons through ECPs. We demonstrate and validate the ECP extensions for complex bonding structures, geometries, and energetics of systems with p-block character (C, O, Al, Si) and apply them to study materials under extreme mechanical loading conditions.

Despite its success, the eFF framework has some limitations, originated from both the design of Pauli potentials and the FSG representation. To overcome these, we develop a new framework of two-level hierarchy that is a more rigorous and accurate successor to the eFF method. The fundamental level, GHA-QM, is based on a new set of Pauli potentials that renders exact QM level of accuracy for any FSG represented electron systems. To achieve this, we start with using exactly derived energy expressions for the same spin electron pair, and fitting a simple functional form, inspired by DFT, against open singlet electron pair curves (H₂ systems). Symmetric and asymmetric scaling factors are then introduced at this level to recover the QM total energies of multiple electron pair systems from the sum of local interactions. To complement the imperfect FSG representation, the AMPERE extension is implemented, and aims at embedding the interactions associated with both the cusp condition and explicit nodal structures. The whole GHA-QM+AMPERE framework is tested on H element, and the preliminary results are promising.

Light-matter Interactions in Semiconductors and Metals: From Nitride Optoelectronics to Quantum Plasmonics

This thesis puts forth a theory-directed approach coupled with spectroscopy aimed at the discovery and understanding of light-matter interactions in semiconductors and metals.

The first part of the thesis presents the discovery and development of Zn-IV nitride materials.The commercial prominence in the optoelectronics industry of tunable semiconductor alloy materials based on nitride semiconductor devices, specifically InGaN, motivates the search for earth-abundant alternatives for use in efficient, high-quality optoelectronic devices. II-IV-N2 compounds, which are closely related to the wurtzite-structured III-N semiconductors, have similar electronic and optical properties to InGaN namely direct band gaps, high quantum efficiencies and large optical absorption coefficients. The choice of different group II and group IV elements provides chemical diversity that can be exploited to tune the structural and electronic properties through the series of alloys. The first theoretical and experimental investigation of the ZnSnxGe1−xN2 series as a replacement for III-nitrides is discussed here.

The second half of the thesis shows ab−initio calculations for surface plasmons and plasmonic hot carrier dynamics. Surface plasmons, electromagnetic modes confined to the surface of a conductor-dielectric interface, have sparked renewed interest because of their quantum nature and their broad range of applications. The decay of surface plasmons is usually a detriment in the field of plasmonics, but the possibility to capture the energy normally lost to heat would open new opportunities in photon sensors, energy conversion devices and switching. A theoretical understanding of plasmon-driven hot carrier generation and relaxation dynamics in the ultrafast regime is presented here. Additionally calculations for plasmon-mediated upconversion as well as an energy-dependent transport model for these non-equilibrium carriers are shown.

Finally, this thesis gives an outlook on the potential of non-equilibrium phenomena in metals and semiconductors for future light-based technologies.

Studies on the role of histones in the structure and function of chromatin

Studies on the dissociation of histones from chromatin by increasing concentrations of sodium deoxycholate (DOC) have shown that histrone II is removed at lowest concentrations of DOC, while slightly higher concentrations remove histones III and IV. Still higher concentrations remove histone I.

The complete separation of chromatin and ¹⁴C-DOC by sucrose sedimentation indicated that the binding of DOC to chromatin is readily and completely reversible.

The dissociation of histones from chromatin by increasing concentrations of related cholanic acids and some of their conjugated derivatives were studied. The results suggested that the driving force for the interaction between the cholanic acid anion and histones is the lowering of the activity coefficient of the cholanic acid anion which occurs when it is partially removed from solution by interaction with hydrophobic regions of the positively charged histones.

The role of histones in the structure of chromatin has been studied by comparing the effects of selective removal of histones from chromatin by increasing concentrations of DOC with those caused by NaCl (removes histone I at lowest concentrations, while higher concentrations remove histones II, III, and IV). Properties studied included thermal denaturation, sedimentation velocity, flow dichroism, relaxation times of molecules oriented in a flow field, and the irreversible disruption of a 130 S, cross-linked component of sheared chromatin. The data indicated that none of the structural or chemical parameters with which these properties are correlated show a dependence on the presence of one particular histone fraction.

The template activity (ability to prime a 0.2 M KC1 DNA-dependent RNA synthesis system catalyzed by E. coli RNA polymerase) increases from that of native chromatin (approximately 25 per cent of that pure DNA) to that of pure DNA in a fashion which shows a nearly linear relationship to the amount of histone coverage of the template. The precipitability of partially dehistonized chromatin samples in 0.15 M NaCl shows a large dependence on the presence of histone I.

The instability of fluids with time dependent heating

The stability of a fluid having a non-uniform temperature stratification is examined analytically for the response of infinitesimal disturbances. The growth rates of disturbances have been established for a semi-infinite fluid for Rayleigh numbers of 10³, 10⁴, and 10⁵ and for Prandtl numbers of 7.0 and 0.7.

The critical Rayleigh number for a semi-infinite fluid, based on the effective fluid depth, is found to be 32, while it is shown that for a finite fluid layer the critical Rayleigh number depends on the rate of heating. The minimum critical Rayleigh number, based on the depth of a fluid layer, is found to be 1340.

The stability of a finite fluid layer is examined for two special forms of heating. The first is constant flux heating, while in the second, the temperature of the lower surface is increased uniformly in time. In both cases, it is shown that for moderate rates of heating the critical Rayleigh number is reduced, over the value for very slow heating, while for very rapid heating the critical Rayleigh number is greatly increased. These results agree with published experimental observations.

The question of steady, non-cellular convection is given qualitative consideration. It is concluded that, although the motion may originate from infinitesimal disturbances during non-uniform heating, the final flow field is intrinsically non-linear.

Polarization-dependent Talbot effect

The term "polarization-dependent Talbot effect" means that the Talbot self-imaging intensity of a high-density grating is different for TE and TM polarization modes. Numerical simulations with the finite-difference time-domain method show that the polarization dependence of the Talbot images is obvious for gratings with period d between 2 lambda and 3 lambda. Such a polarization-dependent difference for TE and TM polarization of, a high-density grating of 630 lines/mm (corresponding to d/lambda = 2.5) is verified through experiments with the scanning near-field optical microscopy technique, in which a He-Ne laser is used as its polarization is changed from the TE mode to the TM mode. The polarization-dependent Talbot effect should help us to understand more clearly the diffraction behavior of a high-density grating in nano-optics and contribute to wide application of the Talbot effect. (c) 2006 Optical Society of America.

Stock assessment of Lates niloticus (L.), Oreochromis niloticus (L.) and Rastrineobola argentea (Pellegrin) using fisheries-dependent data from Tanzania waters of Lake Victoria

Three commercially important fish species, Lates niloticus (L.), Rastrineobola argentea (Pellegrin) and Oreochromis niloticus (L.) that are fished by artisanal fishermen of Lake Victoria, Tanzania part, were studied in Kagera, Mwanza and Mara beaches from October 1997 to July 1999. Catches, effort, exploitation and stock structure were investigated. Beaches for sampling were selected based on importance for landing the above named fish species. The number of boats found on beach that day, the number that lay idle and their means of propulsion were recorded. As many boats as possible were sampled for gear type and gear size. The catches were sorted into species and measured. Variation in the species and size composition of landings was observed between regions, between months and between gears used. The implications of the findings to management are discussed.

Time-dependent monoenergetic neutron transport in two adjacent semi-infinite media

An exact solution to the monoenergetic Boltzmann equation is obtained for the case of a plane isotropic burst of neutrons introduced at the interface separating two adjacent, dissimilar, semi-infinite media. The method of solution used is to remove the time dependence by a Laplace transformation, solve the transformed equation by the normal mode expansion method, and then invert to recover the time dependence.

The general result is expressed as a sum of definite, multiple integrals, one of which contains the uncollided wave of neutrons originating at the source plane. It is possible to obtain a simplified form for the solution at the interface, and certain numerical calculations are made there.

The interface flux in two adjacent moderators is calculated and plotted as a function of time for several moderator materials. For each case it is found that the flux decay curve has an asymptotic slope given accurately by diffusion theory. Furthermore, the interface current is observed to change directions when the scattering and absorption cross sections of the two moderator materials are related in a certain manner. More specifically, the reflection process in two adjacent moderators appears to depend initially on the scattering properties and for long times on the absorption properties of the media.

This analysis contains both the single infinite and semi-infinite medium problems as special cases. The results in these two special cases provide a check on the accuracy of the general solution since they agree with solutions of these problems obtained by separate analyses.

Phase interpretation for polarization-dependent near-field images of high-density gratings

It has been described that the near-field images of a high-density grating at the half self-imaging distance could be different for TE and TM polarization states. We propose that the phases of the diffraction orders play an important role in such polarization dependence. The view is verified through the coincidence of the numerical result of finite-difference time-domain method and the reconstructed results from the rigorous coupled-wave analysis. Field distributions of TE and TM polarizations are given numerically for a grating with period d = 2.3 lambda, which are verified through experiments with the scanning near-field optical microscopy technique. The concept of phase interpretation not only explains the polarization dependence at the half self-imaging distance of gratings with a physical view, but also, it could be widely used to describe the near-field diffraction of a variety of periodic diffractive optical elements whose feature size comparable to the wavelength. (C) 2008 Elsevier B.V. All rights reserved.