Experimental Study and Numerical Simulation of Cellular Structures and Mach Reflection of Gaseous Detonation Wave

In this paper the Deflagration to Detonation Transition (DDT) process of gaseous H-2-O-2 mixture and Mach reflection of gaseous detonation wave on a wedge have been conducted experimentally. The cellular pattern of DDT process and Mach reflection were obtained from experiments with wedge angle theta = 10(0) similar to 40(0) and initial pressure of gaseous mixture 16kPa similar to 26.7kPa. The 2-D numerical simulations of DDT process and Mach reflection of detonation wave were performed by using the simplified ZND model and improved space-time conservation element and solution element (CE/SE) method. The numerical cellular structures were compared with the cellular patterns of soot track. Compared results were shown that it is satisfactory. The characteristic comparisons on Mach reflection of air shock wave and detonation wave were carried also out and their differences were given.

Organizational Structures and Strategies For the Hard Clam Aquaculture Industry in Florida

This study provides guidance on statewide organization for the commercial hard clam culture industry in Florida. The study characterizes the structure of and identifies strategies for successful agricultural and aquacultural organizations designed to provide the resources needed to solve current and projected industry problems. Objectives were to 1) characterize the structure of successful and relevant organizations, 2) identify successful revenue generating strategies, 3) provide the hard clam culture industry with options to help facilitate their organizational decisions, and 4) assist clam growers in Florida in developing an umbrella organizational strategy that will meet their future industry needs. (PDF has 60 pages.)

Uncertain Information Structures and Backward Induction

In everyday economic interactions, it is not clear whether sequential choices are visible or not to other participants: agents might be deluded about opponents'capacity to acquire,interpret or keep track of data, or might simply unexpectedly forget what they previously observed (but not chose). Following this idea, this paper drops the assumption that the information structure of extensive-form games is commonly known; that is, it introduces uncertainty into players' capacity to observe each others' past choices. Using this approach, our main result provides the following epistemic characterisation: if players (i) are rational,(ii) have strong belief in both opponents' rationality and opponents' capacity to observe others' choices, and (iii) have common belief in both opponents' future rationality and op-ponents' future capacity to observe others' choices, then the backward induction outcome obtains. Consequently, we do not require perfect information, and players observing each others' choices is often irrelevant from a strategic point of view. The analysis extends {from generic games with perfect information to games with not necessarily perfect information{the work by Battigalli and Siniscalchi (2002) and Perea (2014), who provide different sufficient epistemic conditions for the backward induction outcome.

Nonstationary response of structures and its application to earthquake engineering

This thesis presents a simplified state-variable method to solve for the nonstationary response of linear MDOF systems subjected to a modulated stationary excitation in both time and frequency domains. The resulting covariance matrix and evolutionary spectral density matrix of the response may be expressed as a product of a constant system matrix and a time-dependent matrix, the latter can be explicitly evaluated for most envelopes currently prevailing in engineering. The stationary correlation matrix of the response may be found by taking the limit of the covariance response when a unit step envelope is used. The reliability analysis can then be performed based on the first two moments of the response obtained.

The method presented facilitates obtaining explicit solutions for general linear MDOF systems and is flexible enough to be applied to different stochastic models of excitation such as the stationary models, modulated stationary models, filtered stationary models, and filtered modulated stationary models and their stochastic equivalents including the random pulse train model, filtered shot noise, and some ARMA models in earthquake engineering. This approach may also be readily incorporated into finite element codes for random vibration analysis of linear structures.

A set of explicit solutions for the response of simple linear structures subjected to modulated white noise earthquake models with four different envelopes are presented as illustration. In addition, the method has been applied to three selected topics of interest in earthquake engineering, namely, nonstationary analysis of primary-secondary systems with classical or nonclassical dampings, soil layer response and related structural reliability analysis, and the effect of the vertical components on seismic performance of structures. For all the three cases, explicit solutions are obtained, dynamic characteristics of structures are investigated, and some suggestions are given for aseismic design of structures.

Wave interactions in periodic structures and periodic dielectric waveguides

This work is concerned with a general analysis of wave interactions in periodic structures and particularly periodic thin film dielectric waveguides.

The electromagnetic wave propagation in an asymmetric dielectric waveguide with a periodically perturbed surface is analyzed in terms of a Floquet mode solution. First order approximate analytical expressions for the space harmonics are obtained. The solution is used to analyze various applications: (1) phase matched second harmonic generation in periodically perturbed optical waveguides; (2) grating couplers and thin film filters; (3) Bragg reflection devices; (4) the calculation of the traveling wave interaction impedance for solid state and vacuum tube optical traveling wave amplifiers which utilize periodic dielectric waveguides. Some of these applications are of interest in the field of integrated optics.

A special emphasis is put on the analysis of traveling wave interaction between electrons and electromagnetic waves in various operation regimes. Interactions with a finite temperature electron beam at the collision-dominated, collisionless, and quantum regimes are analyzed in detail assuming a one-dimensional model and longitudinal coupling.

The analysis is used to examine the possibility of solid state traveling wave devices (amplifiers, modulators), and some monolithic structures of these devices are suggested, designed to operate at the submillimeter-far infrared frequency regime. The estimates of attainable traveling wave interaction gain are quite low (on the order of a few inverse centimeters). However, the possibility of attaining net gain with different materials, structures and operation condition is not ruled out.

The developed model is used to discuss the possibility and the theoretical limitations of high frequency (optical) operation of vacuum electron beam tube; and the relation to other electron-electromagnetic wave interaction effects (Smith-Purcell and Cerenkov radiation and the free electron laser) are pointed out. Finally, the case where the periodic structure is the natural crystal lattice is briefly discussed. The longitudinal component of optical space harmonics in the crystal is calculated and found to be of the order of magnitude of the macroscopic wave, and some comments are made on the possibility of coherent bremsstrahlung and distributed feedback lasers in single crystals.

Direct simulation of proton-coupled electron transfer reaction dynamics and mechanisms

Proton-coupled electron transfer (PCET) reactions are ubiquitous throughout chemistry and biology. However, challenges arise in both the the experimental and theoretical investigation of PCET reactions; the rare-event nature of the reactions and the coupling between quantum mechanical electron- and proton-transfer with the slower classical dynamics of the surrounding environment necessitates the development of robust simulation methodology. In the following dissertation, novel path-integral based methods are developed and employed for the direct simulation of the reaction dynamics and mechanisms of condensed-phase PCET.

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.

Computational Predictions of G Protein-Coupled Receptor Structures and Binding Sites

G protein-coupled receptors (GPCRs) are the largest family of proteins within the human genome. They consist of seven transmembrane (TM) helices, with a N-terminal region of varying length and structure on the extracellular side, and a C-terminus on the intracellular side. GPCRs are involved in transmitting extracellular signals to cells, and as such are crucial drug targets. Designing pharmaceuticals to target GPCRs is greatly aided by full-atom structural information of the proteins. In particular, the TM region of GPCRs is where small molecule ligands (much more bioavailable than peptide ligands) typically bind to the receptors. In recent years nearly thirty distinct GPCR TM regions have been crystallized. However, there are more than 1,000 GPCRs, leaving the vast majority of GPCRs with limited structural information. Additionally, GPCRs are known to exist in a myriad of conformational states in the body, rendering the static x-ray crystal structures an incomplete reflection of GPCR structures. In order to obtain an ensemble of GPCR structures, we have developed the GEnSeMBLE procedure to rapidly sample a large number of variations of GPCR helix rotations and tilts. The lowest energy GEnSeMBLE structures are then docked to small molecule ligands and optimized. The GPCR family consists of five subfamilies with little to no sequence homology between them: class A, B1, B2, C, and Frizzled/Taste2. Almost all of the GPCR crystal structures have been of class A GPCRs, and much is known about their conserved interactions and binding sites. In this work we particularly focus on class B1 GPCRs, and aim to understand that family’s interactions and binding sites both to small molecules and their native peptide ligands. Specifically, we predict the full atom structure and peptide binding site of the glucagon-like peptide receptor and the TM region and small molecule binding sites for eight other class B1 GPCRs: CALRL, CRFR1, GIPR, GLR, PACR, PTH1R, VIPR1, and VIPR2. Our class B1 work reveals multiple conserved interactions across the B1 subfamily as well as a consistent small molecule binding site centrally located in the TM bundle. Both the interactions and the binding sites are distinct from those seen in the more well-characterized class A GPCRs, and as such our work provides a strong starting point for drug design targeting class B1 proteins. We also predict the full structure of CXCR4 bound to a small molecule, a class A GPCR that was not closely related to any of the class A GPCRs at the time of the work.

Kinetics and mechanisms of adsorption of Escherichia coli bacteriophage T_4 to activated carbon

A study was conducted on the adsorption of Escherichia coli bacteriophage T₄ to activated carbon. Preliminary adsorption experiments were also made with poliovirus Type III. The effectiveness of such adsorbents as diatomaceous earth, Ottawa sand, and coconut charcoal was also tested for virus adsorption.

The kinetics of adsorption were studied in an agitated solution containing virus and carbon. The mechanism of attachment and site characteristics were investigated by varying pH and ionic strength and using site-blocking reagents.

Plaque assay procedures were developed for bacteriophage T₄ on Escherichia coli cells and poliovirus Type III on monkey kidney cells. Factors influencing the efficiency of plaque formation were investigated.

The kinetics of bacteriophage T₄ adsorption to activated carbon can be described by a reversible second-order equation. The reaction order was first order with respect to both virus and carbon concentration. This kinetic representation, however, is probably incorrect at optimum adsorption conditions, which occurred at a pH of 7.0 and ionic strength of 0.08. At optimum conditions the adsorption rate was satisfactorily described by a diffusion-limited process. Interpretation of adsorption data by a development of the diffusion equation for Langmuir adsorption yielded a diffusion coefficient of 12 X 10^-8 cm²/sec for bacteriophage T₄. This diffusion coefficient is in excellent agreement with the accepted value of 8 X 10^-8 cm²/sec. A diffusion-limited theory may also represent adsorption at conditions other than the maximal. A clear conclusion on the limiting process cannot be made.

Adsorption of bacteriophage T₄ to activated carbon obeys the Langmuir isotherm and is thermodynamically reversible. Thus virus is not inactivated by adsorption. Adsorption is unimolecular with very inefficient use of the available carbon surface area. The virus is probably completely excluded from pores due to its size.

Adsorption is of a physical nature and independent of temperature. Attraction is due to electrostatic forces between the virus and carbon. Effects of pH and ionic strength indicated that carboxyl groups, amino groups, and the virus's tail fibers are involved in the attachment of virus to carbon. The active sites on activated carbon for adsorption of bacteriophage T₄ are carboxyl groups. Adsorption can be completely blocked by esterifying these groups.

Simulations and mechanisms of subtropical low-cloud response to climate change

This thesis focuses on improving the simulation skills and the theoretical understanding of the subtropical low cloud response to climate change.

First, an energetically consistent forcing framework is designed and implemented for the large eddy simulation (LES) of the low-cloud response to climate change. The three representative current-day subtropical low cloud regimes of cumulus (Cu), cumulus-over-stratocumulus, and stratocumulus (Sc) are all well simulated with this framework, and results are comparable to the conventional fixed-SST approach. However, the cumulus response to climate warming subject to energetic constraints differs significantly from the conventional approach with fixed SST. Under the energetic constraint, the subtropics warm less than the tropics, since longwave (LW) cooling is more efficient with the drier subtropical free troposphere. The surface latent heat flux (LHF) also increases only weakly subject to the surface energetic constraint. Both factors contribute to an increased estimated inversion strength (EIS), and decreased inversion height. The decreased Cu-depth contributes to a decrease of liquid water path (LWP) and weak positive cloud feedback. The conventional fixed-SST approach instead simulates a strong increase in LHF and deepening of the Cu layer, leading to a weakly negative cloud feedback. This illustrates the importance of energetic constraints to the simulation and understanding of the sign and magnitude of low-cloud feedback.

Second, an extended eddy-diffusivity mass-flux (EDMF) closure for the unified representation of sub-grid scale (SGS) turbulence and convection processes in general circulation models (GCM) is presented. The inclusion of prognostic terms and the elimination of the infinitesimal updraft fraction assumption makes it more flexible for implementation in models across different scales. This framework can be consistently extended to formulate multiple updrafts and downdrafts, as well as variances and covariances. It has been verified with LES in different boundary layer regimes in the current climate, and further development and implementation of this closure may help to improve our simulation skills and understanding of low-cloud feedback through GCMs.

Normal structures and automorphism groups of t-designs

Combinatorial configurations known as t-designs are studied. These are pairs ˂B, ∏˃, where each element of B is a k-subset of ∏, and each t-design occurs in exactly λ elements of B, for some fixed integers k and λ. A theory of internal structure of t-designs is developed, and it is shown that any t-design can be decomposed in a natural fashion into a sequence of “simple” subdesigns. The theory is quite similar to the analysis of a group with respect to its normal subgroups, quotient groups, and homomorphisms. The analogous concepts of normal subdesigns, quotient designs, and design homomorphisms are all defined and used.

This structure theory is then applied to the class of t-designs whose automorphism groups are transitive on sets of t points. It is shown that if G is a permutation group transitive on sets of t letters and ф is any set of letters, then images of ф under G form a t-design whose parameters may be calculated from the group G. Such groups are discussed, especially for the case t = 2, and the normal structure of such designs is considered. Theorem 2.2.12 gives necessary and sufficient conditions for a t-design to be simple, purely in terms of the automorphism group of the design. Some constructions are given.

Finally, 2-designs with k = 3 and λ = 2 are considered in detail. These designs are first considered in general, with examples illustrating some of the configurations which can arise. Then an attempt is made to classify all such designs with an automorphism group transitive on pairs of points. Many cases are eliminated of reduced to combinations of Steiner triple systems. In the remaining cases, the simple designs are determined to consist of one infinite class and one exceptional case.

Upconversion luminescence and mechanisms of Tm3+/Yb3+-codoped oxyhalide tellurite glasses

To obtain efficient blue upconversion laser glasses, upconversion luminescence and mechanisms of Tm3+/Yb3+-codoped oxyhalide tellurite glasses were investigated under 980nm excitation. The results showed that upconversion blue and red emission intensities of Tm3+ first increase, reach its maximum at TM2O3% =0.1 mol%, and then decrease with increasing Tm2O3 content. The effect of TM2O3 content on upconversion intensity is discussed, and possible effect mechanisms are evaluated. The investigated results were conducing to increase upconversion luminescence efficiency of Tm3+. (c) 2005 Elsevier B.V. All rights reserved.

Upconversion luminescence and mechanisms in Yb3+-sensitized Tm3+-doped oxyhalide tellurite glasses

Effect of Yb2O3 content on upconversion luminescence and mechanisms in Yb3+-sensitized Tm3+-doped oxyhalide tellurite glasses were investigated under 980 nm excitation. Intense blue and relatively weak red upconversion emission centered at 476 and 649nm corresponding to the transitions (1)G(4) -> H-3(6) and (1)G(4) -> H-3(4) of Tm3+, respectively, are simultaneously observed at room temperature. The results show that upconversion blue and red emission intensities of Tm3+ first increase, reach its maximum at Yb2O3% = 3 mol%, and then decrease with increasing Yb2O3 content. The effect of Yb2O3 content on upconversion intensity is discussed, and possible effect mechanisms are evaluated. The investigated results were conducing to increase upconversion luminescence efficiency of Tm3+. (c) 2005 Elsevier B.V. All rights reserved.