Observations and Modeling of Tropical Planetary Atmospheres

This thesis is a comprised of three different projects within the topic of tropical atmospheric dynamics. First, I analyze observations of thermal radiation from Saturn’s atmosphere and from them, determine the latitudinal distribution of ammonia vapor near the 1.5-bar pressure level. The most prominent feature of the observations is the high brightness temperature of Saturn’s subtropical latitudes on either side of the equator. After comparing the observations to a microwave radiative transfer model, I find that these subtropical bands require very low ammonia relative humidity below the ammonia cloud layer in order to achieve the high brightness temperatures observed. We suggest that these bright subtropical bands represent dry zones created by a meridionally overturning circulation.

Second, I use a dry atmospheric general circulation model to study equatorial superrotation in terrestrial atmospheres. A wide range of atmospheres are simulated by varying three parameters: the pole-equator radiative equilibrium temperature contrast, the convective lapse rate, and the planetary rotation rate. A scaling theory is developed that establishes conditions under which superrotation occurs in terrestrial atmospheres. The scaling arguments show that superrotation is favored when the off-equatorial baroclinicity and planetary rotation rates are low. Similarly, superrotation is favored when the convective heating strengthens, which may account for the superrotation seen in extreme global-warming simulations.

Third, I use a moist slab-ocean general circulation model to study the impact of a zonally-symmetric continent on the distribution of monsoonal precipitation. I show that adding a hemispheric asymmetry in surface heat capacity is sufficient to cause symmetry breaking in both the spatial and temporal distribution of precipitation. This spatial symmetry breaking can be understood from a large-scale energetic perspective, while the temporal symmetry breaking requires consideration of the dynamical response to the heat capacity asymmetry and the seasonal cycle of insolation. Interestingly, the idealized monsoonal precipitation bears resemblance to precipitation in the Indian monsoon sector, suggesting that this work may provide insight into the causes of the temporally asymmetric distribution of precipitation over southeast Asia.

Analog VLSI-based, neuromorphic sensorimotor systems: modeling the primate oculomotor system

Using neuromorphic analog VLSI techniques for modeling large neural systems has several advantages over software techniques. By designing massively-parallel analog circuit arrays which are ubiquitous in neural systems, analog VLSI models are extremely fast, particularly when local interactions are important in the computation. While analog VLSI circuits are not as flexible as software methods, the constraints posed by this approach are often very similar to the constraints faced by biological systems. As a result, these constraints can offer many insights into the solutions found by evolution. This dissertation describes a hardware modeling effort to mimic the primate oculomotor system which requires both fast sensory processing and fast motor control. A one-dimensional hardware model of the primate eye has been built which simulates the physical dynamics of the biological system. It is driven by analog VLSI circuits mimicking brainstem and cortical circuits that control eye movements. In this framework, a visually-triggered saccadic system is demonstrated which generates averaging saccades. In addition, an auditory localization system, based on the neural circuits of the barn owl, is used to trigger saccades to acoustic targets in parallel with visual targets. Two different types of learning are also demonstrated on the saccadic system using floating-gate technology allowing the non-volatile storage of analog parameters directly on the chip. Finally, a model of visual attention is used to select and track moving targets against textured backgrounds, driving both saccadic and smooth pursuit eye movements to maintain the image of the target in the center of the field of view. This system represents one of the few efforts in this field to integrate both neuromorphic sensory processing and motor control in a closed-loop fashion.

Modeling and analysis of hysteretic structural behavior

For damaging response, the force-displacement relationship of a structure is highly nonlinear and history-dependent. For satisfactory analysis of such behavior, it is important to be able to characterize and to model the phenomenon of hysteresis accurately. A number of models have been proposed for response studies of hysteretic structures, some of which are examined in detail in this thesis. There are two popular classes of models used in the analysis of curvilinear hysteretic systems. The first is of the distributed element or assemblage type, which models the physical behavior of the system by using well-known building blocks. The second class of models is of the differential equation type, which is based on the introduction of an extra variable to describe the history dependence of the system.

Owing to their mathematical simplicity, the latter models have been used extensively for various applications in structural dynamics, most notably in the estimation of the response statistics of hysteretic systems subjected to stochastic excitation. But the fundamental characteristics of these models are still not clearly understood. A response analysis of systems using both the Distributed Element model and the differential equation model when subjected to a variety of quasi-static and dynamic loading conditions leads to the following conclusion: Caution must be exercised when employing the models belonging to the second class in structural response studies as they can produce misleading results.

The Massing's hypothesis, originally proposed for steady-state loading, can be extended to general transient loading as well, leading to considerable simplification in the analysis of the Distributed Element models. A simple, nonparametric identification technique is also outlined, by means of which an optimal model representation involving one additional state variable is determined for hysteretic systems.

2D modeling of lower mantle structure with WKM synthetics

The Earth is very heterogeneous, especially in the region close to the surface of the Earth, and in regions close to the core-mantle boundary (CMB). The lowermost mantle (bottom 300km of the mantle) is the place for fast anomaly (3% faster S velocity than PREM, modeled from Scd), for slow anomaly (-3% slower S velocity than PREM, modeled from S,ScS), for extreme anomalous structure (ultra-low velocity zone, 30% lower inS velocity, 10% lower in P velocity). Strong anomaly with larger dimension is also observed beneath Africa and Pacific, originally modeled from travel time of S, SKS and ScS. Given the heterogeneous nature of the earth, more accurate approach (than travel time) has to be applied to study the details of various anomalous structures, and matching waveform with synthetic seismograms has proven effective in constraining the velocity structures. However, it is difficult to make synthetic seismograms in more than 1D cases where no exact analytical solution is possible. Numerical methods like finite difference or finite elements are too time consuming in modeling body waveforms. We developed a 2D synthetic algorithm, which is extended from 1D generalized ray theory (GRT), to make synthetic seismograms efficiently (each seismogram per minutes). This 2D algorithm is related to WKB approximation, but is based on different principles, it is thus named to be WKM, i.e., WKB modified. WKM has been applied to study the variation of fast D" structure beneath the Caribbean sea, to study the plume beneath Africa. WKM is also applied to study PKP precursors which is a very important seismic phase in modeling lower mantle heterogeneity. By matching WKM synthetic seismograms with various data, we discovered and confirmed that (a) The D" beneath Caribbean varies laterally, and the variation is best revealed with Scd+Sab beyond 88 degree where Sed overruns Sab. (b) The low velocity structure beneath Africa is about 1500 km in height, at least 1000km in width, and features 3% reduced S velocity. The low velocity structure is a combination of a relatively thin, low velocity layer (200 km thick or less) beneath the Atlantic, then rising very sharply into mid mantle towards Africa. (c) At the edges of this huge Africa low velocity structures, ULVZs are found by modeling the large separation between S and ScS beyond 100 degree. The ULVZ to the eastern boundary was discovered with SKPdS data, and later is confirmed by PKP precursor data. This is the first time that ULVZ is verified with distinct seismic phase.

Digested sludge: delineation and modeling for ocean disposal

Experimental work was performed to delineate the system of digested sludge particles and associated trace metals and also to measure the interactions of sludge with seawater. Particle-size and particle number distributions were measured with a Coulter Counter. Number counts in excess of 10¹² particles per liter were found in both the City of Los Angeles Hyperion mesophilic digested sludge and the Los Angeles County Sanitation Districts (LACSD) digested primary sludge. More than 90 percent of the particles had diameters less than 10 microns.

Total and dissolved trace metals (Ag, Cd, Cr, Cu, Fe, Mn, Ni, Pb, and Zn) were measured in LACSD sludge. Manganese was the only metal whose dissolved fraction exceeded one percent of the total metal. Sedimentation experiments for several dilutions of LACSD sludge in seawater showed that the sedimentation velocities of the sludge particles decreased as the dilution factor increased. A tenfold increase in dilution shifted the sedimentation velocity distribution by an order of magnitude. Chromium, Cu, Fe, Ni, Pb, and Zn were also followed during sedimentation. To a first approximation these metals behaved like the particles.

Solids and selected trace metals (Cr, Cu, Fe, Ni, Pb, and Zn) were monitored in oxic mixtures of both Hyperion and LACSD sludges for periods of 10 to 28 days. Less than 10 percent of the filterable solids dissolved or were oxidized. Only Ni was mobilized away from the particles. The majority of the mobilization was complete in less than one day.

The experimental data of this work were combined with oceanographic, biological, and geochemical information to propose and model the discharge of digested sludge to the San Pedro and Santa Monica Basins. A hydraulic computer simulation for a round buoyant jet in a density stratified medium showed that discharges of sludge effluent mixture at depths of 730 m would rise no more than 120 m. Initial jet mixing provided dilution estimates of 450 to 2600. Sedimentation analyses indicated that the solids would reach the sediments within 10 km of the point discharge.

Mass balances on the oxidizable chemical constituents in sludge indicated that the nearly anoxic waters of the basins would become wholly anoxic as a result of proposed discharges. From chemical-equilibrium computer modeling of the sludge digester and dilutions of sludge in anoxic seawater, it was predicted that the chemistry of all trace metals except Cr and Mn will be controlled by the precipitation of metal sulfide solids. This metal speciation held for dilutions up to 3000.

The net environmental impacts of this scheme should be salutary. The trace metals in the sludge should be immobilized in the anaerobic bottom sediments of the basins. Apparently no lifeforms higher than bacteria are there to be disrupted. The proposed deep-water discharges would remove the need for potentially expensive and energy-intensive land disposal alternatives and would end the discharge to the highly productive water near the ocean surface.

Wind-driven desertification: process modeling, remote monitoring, and forecasting

Arid and semiarid landscapes comprise nearly a third of the Earth's total land surface. These areas are coming under increasing land use pressures. Despite their low productivity these lands are not barren. Rather, they consist of fragile ecosystems vulnerable to anthropogenic disturbance.

The purpose of this thesis is threefold: (I) to develop and test a process model of wind-driven desertification, (II) to evaluate next-generation process-relevant remote monitoring strategies for use in arid and semiarid regions, and (III) to identify elements for effective management of the world's drylands.

In developing the process model of wind-driven desertification in arid and semiarid lands, field, remote sensing, and modeling observations from a degraded Mojave Desert shrubland are used. This model focuses on aeolian removal and transport of dust, sand, and litter as the primary mechanisms of degradation: killing plants by burial and abrasion, interrupting natural processes of nutrient accumulation, and allowing the loss of soil resources by abiotic transport. This model is tested in field sampling experiments at two sites and is extended by Fourier Transform and geostatistical analysis of high-resolution imagery from one site.

Next, the use of hyperspectral remote sensing data is evaluated as a substantive input to dryland remote monitoring strategies. In particular, the efficacy of spectral mixture analysis (SMA) in discriminating vegetation and soil types and detennining vegetation cover is investigated. The results indicate that hyperspectral data may be less useful than often thought in determining vegetation parameters. Its usefulness in determining soil parameters, however, may be leveraged by developing simple multispectral classification tools that can be used to monitor desertification.

Finally, the elements required for effective monitoring and management of arid and semiarid lands are discussed. Several large-scale multi-site field experiments are proposed to clarify the role of wind as a landscape and degradation process in dry lands. The role of remote sensing in monitoring the world's drylands is discussed in terms of optimal remote sensing platform characteristics and surface phenomena which may be monitored in order to identify areas at risk of desertification. A desertification indicator is proposed that unifies consideration of environmental and human variables.

Computational modeling and psychophysics in low- and mid-level vision

This thesis addresses a series of topics related to the question of how people find the foreground objects from complex scenes. With both computer vision modeling, as well as psychophysical analyses, we explore the computational principles for low- and mid-level vision.

We first explore the computational methods of generating saliency maps from images and image sequences. We propose an extremely fast algorithm called Image Signature that detects the locations in the image that attract human eye gazes. With a series of experimental validations based on human behavioral data collected from various psychophysical experiments, we conclude that the Image Signature and its spatial-temporal extension, the Phase Discrepancy, are among the most accurate algorithms for saliency detection under various conditions.

In the second part, we bridge the gap between fixation prediction and salient object segmentation with two efforts. First, we propose a new dataset that contains both fixation and object segmentation information. By simultaneously presenting the two types of human data in the same dataset, we are able to analyze their intrinsic connection, as well as understanding the drawbacks of today’s “standard” but inappropriately labeled salient object segmentation dataset. Second, we also propose an algorithm of salient object segmentation. Based on our novel discoveries on the connections of fixation data and salient object segmentation data, our model significantly outperforms all existing models on all 3 datasets with large margins.

In the third part of the thesis, we discuss topics around the human factors of boundary analysis. Closely related to salient object segmentation, boundary analysis focuses on delimiting the local contours of an object. We identify the potential pitfalls of algorithm evaluation for the problem of boundary detection. Our analysis indicates that today’s popular boundary detection datasets contain significant level of noise, which may severely influence the benchmarking results. To give further insights on the labeling process, we propose a model to characterize the principles of the human factors during the labeling process.

The analyses reported in this thesis offer new perspectives to a series of interrelating issues in low- and mid-level vision. It gives warning signs to some of today’s “standard” procedures, while proposing new directions to encourage future research.

The Madden-Julian Oscillation : observation, modeling, and theory

The Madden-Julian Oscillation (MJO) is a pattern of intense rainfall and associated planetary-scale circulations in the tropical atmosphere, with a recurrence interval of 30-90 days. Although the MJO was first discovered 40 years ago, it is still a challenge to simulate the MJO in general circulation models (GCMs), and even with simple models it is difficult to agree on the basic mechanisms. This deficiency is mainly due to our poor understanding of moist convection—deep cumulus clouds and thunderstorms, which occur at scales that are smaller than the resolution elements of the GCMs. Moist convection is the most important mechanism for transporting energy from the ocean to the atmosphere. Success in simulating the MJO will improve our understanding of moist convection and thereby improve weather and climate forecasting.

We address this fundamental subject by analyzing observational datasets, constructing a hierarchy of numerical models, and developing theories. Parameters of the models are taken from observation, and the simulated MJO fits the data without further adjustments. The major findings include: 1) the MJO may be an ensemble of convection events linked together by small-scale high-frequency inertia-gravity waves; 2) the eastward propagation of the MJO is determined by the difference between the eastward and westward phase speeds of the waves; 3) the planetary scale of the MJO is the length over which temperature anomalies can be effectively smoothed by gravity waves; 4) the strength of the MJO increases with the typical strength of convection, which increases in a warming climate; 5) the horizontal scale of the MJO increases with the spatial frequency of convection; and 6) triggered convection, where potential energy accumulates until a threshold is reached, is important in simulating the MJO. Our findings challenge previous paradigms, which consider the MJO as a large-scale mode, and point to ways for improving the climate models.

Progress in numerical modeling of non-premixed combustion

Progress is made on the numerical modeling of both laminar and turbulent non-premixed flames. Instead of solving the transport equations for the numerous species involved in the combustion process, the present study proposes reduced-order combustion models based on local flame structures.

For laminar non-premixed flames, curvature and multi-dimensional diffusion effects are found critical for the accurate prediction of sooting tendencies. A new numerical model based on modified flamelet equations is proposed. Sooting tendencies are calculated numerically using the proposed model for a wide range of species. These first numerically-computed sooting tendencies are in good agreement with experimental data. To further quantify curvature and multi-dimensional effects, a general flamelet formulation is derived mathematically. A budget analysis of the general flamelet equations is performed on an axisymmetric laminar diffusion flame. A new chemistry tabulation method based on the general flamelet formulation is proposed. This new tabulation method is applied to the same flame and demonstrates significant improvement compared to previous techniques.

For turbulent non-premixed flames, a new model to account for chemistry-turbulence interactions is proposed. %It is found that these interactions are not important for radicals and small species, but substantial for aromatic species. The validity of various existing flamelet-based chemistry tabulation methods is examined, and a new linear relaxation model is proposed for aromatic species. The proposed relaxation model is validated against full chemistry calculations. To further quantify the importance of aromatic chemistry-turbulence interactions, Large-Eddy Simulations (LES) have been performed on a turbulent sooting jet flame. %The aforementioned relaxation model is used to provide closure for the chemical source terms of transported aromatic species. The effects of turbulent unsteadiness on soot are highlighted by comparing the LES results with a separate LES using fully-tabulated chemistry. It is shown that turbulent unsteady effects are of critical importance for the accurate prediction of not only the inception locations, but also the magnitude and fluctuations of soot.

Analyses of planetary atmospheres across the spectrum : from Titan to exoplanets

Planetary atmospheres exist in a seemingly endless variety of physical and chemical environments. There are an equally diverse number of methods by which we can study and characterize atmospheric composition. In order to better understand the fundamental chemistry and physical processes underlying all planetary atmospheres, my research of the past four years has focused on two distinct topics. First, I focused on the data analysis and spectral retrieval of observations obtained by the Ultraviolet Imaging Spectrograph (UVIS) instrument onboard the Cassini spacecraft while in orbit around Saturn. These observations consisted of stellar occultation measurements of Titan's upper atmosphere, probing the chemical composition in the region 300 to 1500 km above Titan's surface. I examined the relative abundances of Titan's two most prevalent chemical species, nitrogen and methane. I also focused on the aerosols that are formed through chemistry involving these two major species, and determined the vertical profiles of aerosol particles as a function of time and latitude. Moving beyond our own solar system, my second topic of investigation involved analysis of infra-red light curves from the Spitzer space telescope, obtained as it measured the light from stars hosting planets of their own. I focused on both transit and eclipse modeling during Spitzer data reduction and analysis. In my initial work, I utilized the data to search for transits of planets a few Earth masses in size. In more recent research, I analyzed secondary eclipses of three exoplanets and constrained the range of possible temperatures and compositions of their atmospheres.

Discrete Modeling of Granular Media: A NURBS-based Approach

This dissertation is concerned with the development of a new discrete element method (DEM) based on Non-Uniform Rational Basis Splines (NURBS). With NURBS, the new DEM is able to capture sphericity and angularity, the two particle morphological measures used in characterizing real grain geometries. By taking advantage of the parametric nature of NURBS, the Lipschitzian dividing rectangle (DIRECT) global optimization procedure is employed as a solution procedure to the closest-point projection problem, which enables the contact treatment of non-convex particles. A contact dynamics (CD) approach to the NURBS-based discrete method is also formulated. By combining particle shape flexibility, properties of implicit time-integration, and non-penetrating constraints, we target applications in which the classical DEM either performs poorly or simply fails, i.e., in granular systems composed of rigid or highly stiff angular particles and subjected to quasistatic or dynamic flow conditions. The CD implementation is made simple by adopting a variational framework, which enables the resulting discrete problem to be readily solved using off-the-shelf mathematical programming solvers. The capabilities of the NURBS-based DEM are demonstrated through 2D numerical examples that highlight the effects of particle morphology on the macroscopic response of granular assemblies under quasistatic and dynamic flow conditions, and a 3D characterization of material response in the shear band of a real triaxial specimen.

Source characteristics of recent and historic earthquakes in Central and Southern California: results from forward modeling

The long- and short-period body waves of a number of moderate earthquakes occurring in central and southern California recorded at regional (200-1400 km) and teleseismic (> 30°) distances are modeled to obtain the source parameters-focal mechanism, depth, seismic moment, and source time history. The modeling is done in the time domain using a forward modeling technique based on ray summation. A simple layer over a half space velocity model is used with additional layers being added if necessary-for example, in a basin with a low velocity lid.

The earthquakes studied fall into two geographic regions: 1) the western Transverse Ranges, and 2) the western Imperial Valley. Earthquakes in the western Transverse Ranges include the 1987 Whittier Narrows earthquake, several offshore earthquakes that occurred between 1969 and 1981, and aftershocks to the 1983 Coalinga earthquake (these actually occurred north of the Transverse Ranges but share many characteristics with those that occurred there). These earthquakes are predominantly thrust faulting events with the average strike being east-west, but with many variations. Of the six earthquakes which had sufficient short-period data to accurately determine the source time history, five were complex events. That is, they could not be modeled as a simple point source, but consisted of two or more subevents. The subevents of the Whittier Narrows earthquake had different focal mechanisms. In the other cases, the subevents appear to be the same, but small variations could not be ruled out.

The recent Imperial Valley earthquakes modeled include the two 1987 Superstition Hills earthquakes and the 1969 Coyote Mountain earthquake. All are strike-slip events, and the second 1987 earthquake is a complex event With non-identical subevents.

In all the earthquakes studied, and particularly the thrust events, constraining the source parameters required modeling several phases and distance ranges. Teleseismic P waves could provide only approximate solutions. P_(nl) waves were probably the most useful phase in determining the focal mechanism, with additional constraints supplied by the SH waves when available. Contamination of the SH waves by shear-coupled PL waves was a frequent problem. Short-period data were needed to obtain the source time function.

In addition to the earthquakes mentioned above, several historic earthquakes were also studied. Earthquakes that occurred before the existence of dense local and worldwide networks are difficult to model due to the sparse data set. It has been noticed that earthquakes that occur near each other often produce similar waveforms implying similar source parameters. By comparing recent well studied earthquakes to historic earthquakes in the same region, better constraints can be placed on the source parameters of the historic events.

The Lompoc earthquake (M=7) of 1927 is the largest offshore earthquake to occur in California this century. By direct comparison of waveforms and amplitudes with the Coalinga and Santa Lucia Banks earthquakes, the focal mechanism (thrust faulting on a northwest striking fault) and long-period seismic moment (10^(26) dyne cm) can be obtained. The S-P travel times are consistent with an offshore location, rather than one in the Hosgri fault zone.

Historic earthquakes in the western Imperial Valley were also studied. These events include the 1942 and 1954 earthquakes. The earthquakes were relocated by comparing S-P and R-S times to recent earthquakes. It was found that only minor changes in the epicenters were required but that the Coyote Mountain earthquake may have been more severely mislocated. The waveforms as expected indicated that all the events were strike-slip. Moment estimates were obtained by comparing the amplitudes of recent and historic events at stations which recorded both. The 1942 event was smaller than the 1968 Borrego Mountain earthquake although some previous studies suggested the reverse. The 1954 and 1937 earthquakes had moments close to the expected value. An aftershock of the 1942 earthquake appears to be larger than previously thought.

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.

Characterization and modeling of premixed turbulent n-heptane flames in the thin reaction zone regime

n-heptane/air premixed turbulent flames in the high-Karlovitz portion of the thin reaction zone regime are characterized and modeled in this thesis using Direct Numerical Simulations (DNS) with detailed chemistry. In order to perform these simulations, a time-integration scheme that can efficiently handle the stiffness of the equations solved is developed first. A first simulation with unity Lewis number is considered in order to assess the effect of turbulence on the flame in the absence of differential diffusion. A second simulation with non-unity Lewis numbers is considered to study how turbulence affects differential diffusion. In the absence of differential diffusion, minimal departure from the 1D unstretched flame structure (species vs. temperature profiles) is observed. In the non-unity Lewis number case, the flame structure lies between that of 1D unstretched flames with "laminar" non-unity Lewis numbers and unity Lewis number. This is attributed to effective Lewis numbers resulting from intense turbulent mixing and a first model is proposed. The reaction zone is shown to be thin for both flames, yet large chemical source term fluctuations are observed. The fuel consumption rate is found to be only weakly correlated with stretch, although local extinctions in the non-unity Lewis number case are well correlated with high curvature. These results explain the apparent turbulent flame speeds. Other variables that better correlate with this fuel burning rate are identified through a coordinate transformation. It is shown that the unity Lewis number turbulent flames can be accurately described by a set of 1D (in progress variable space) flamelet equations parameterized by the dissipation rate of the progress variable. In the non-unity Lewis number flames, the flamelet equations suggest a dependence on a second parameter, the diffusion of the progress variable. A new tabulation approach is proposed for the simulation of such flames with these dimensionally-reduced manifolds.

Advancements in jet turbulence and noise modeling: accurate one-way solutions and empirical evaluation of the nonlinear forcing of wavepackets

Jet noise reduction is an important goal within both commercial and military aviation. Although large-scale numerical simulations are now able to simultaneously compute turbulent jets and their radiated sound, lost-cost, physically-motivated models are needed to guide noise-reduction efforts. A particularly promising modeling approach centers around certain large-scale coherent structures, called wavepackets, that are observed in jets and their radiated sound. The typical approach to modeling wavepackets is to approximate them as linear modal solutions of the Euler or Navier-Stokes equations linearized about the long-time mean of the turbulent flow field. The near-field wavepackets obtained from these models show compelling agreement with those educed from experimental and simulation data for both subsonic and supersonic jets, but the acoustic radiation is severely under-predicted in the subsonic case. This thesis contributes to two aspects of these models. First, two new solution methods are developed that can be used to efficiently compute wavepackets and their acoustic radiation, reducing the computational cost of the model by more than an order of magnitude. The new techniques are spatial integration methods and constitute a well-posed, convergent alternative to the frequently used parabolized stability equations. Using concepts related to well-posed boundary conditions, the methods are formulated for general hyperbolic equations and thus have potential applications in many fields of physics and engineering. Second, the nonlinear and stochastic forcing of wavepackets is investigated with the goal of identifying and characterizing the missing dynamics responsible for the under-prediction of acoustic radiation by linear wavepacket models for subsonic jets. Specifically, we use ensembles of large-eddy-simulation flow and force data along with two data decomposition techniques to educe the actual nonlinear forcing experienced by wavepackets in a Mach 0.9 turbulent jet. Modes with high energy are extracted using proper orthogonal decomposition, while high gain modes are identified using a novel technique called empirical resolvent-mode decomposition. In contrast to the flow and acoustic fields, the forcing field is characterized by a lack of energetic coherent structures. Furthermore, the structures that do exist are largely uncorrelated with the acoustic field. Instead, the forces that most efficiently excite an acoustic response appear to take the form of random turbulent fluctuations, implying that direct feedback from nonlinear interactions amongst wavepackets is not an essential noise source mechanism. This suggests that the essential ingredients of sound generation in high Reynolds number jets are contained within the linearized Navier-Stokes operator rather than in the nonlinear forcing terms, a conclusion that has important implications for jet noise modeling.