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.

Prescription for optimizing holograms in LiNbO3 : Fe : Mn

The photorefractive holographic dynamics of grating formation in photochromic doubly doped LiNbO3:Fe:Mn crystal is studied numerically and analytically in terms of the two-center model of Kukhtarev Et al. [Ferroelectrics 22, 949 (1979)]. The relations among the recorded and fixed space-charge fields and the doping densities, the oxidation-reduction states of the fields, and the intensities of UV-sensitizing and red recording beams are studied. Important conditions and effects are feued, and an optimal prescription for material doping and oxidation-reduction processing is suggested in which the crystal can be strongly oxidized and the Mn-doping density is smaller than the Fe-doping density. (C) 2000 Optical Society of America. OCIS codes: 050.7330, 190.5330, 090.2900.

Effect of absorption on the diffraction efficiency in Fe : LiNbO3 crystal with 90 degrees recording geometry

In this paper the saturated diffraction efficiency has been optimized by considering the effect of the absorption of the recording light on a crossed-beam grating with 90 degrees recording geometry in Fe:LiNbO3 crystals. The dependence of saturated diffraction efficiency on the doping levels with a known oxidation-reduction state, as well as the dependence of saturated diffraction efficiency on oxidation-reduction state with known doping levels, has been investigated. Two competing effects on the saturated diffraction efficiency were discussed, and the intensity profile of the diffracted beam at the output boundary has also been investigated. The results show that the maximal saturated diffraction efficiency can be obtained in crystals with moderate doping levels and modest oxidation state. An experimental verification is performed and the results are consistent with those of the theoretical calculation.

Electrochromic effect in domain-inversion process LiNbO3 : Ru : Fe crystals

A reversible electrochromic effect accompanying domain-inversion during the electrical poling process in LiNbO3: Ru: Fe crystals at room temperature has been observed. In electrode area, both electrochromism and domain-inversion occur alternately, and electrochromism is also reversible during back-switch poling, which is experimentally verified and whose mechanism is briefly explained using a microstructure ferroelectric model. In addition, because of the enhancing elcctrochromic effect, different from the undoped LiNbO3 crystals, the coercive riled (21.0 kV/mm or so) measured in LiNbO3: Ru: Fe is lower than its breakdown field, thus providing a possible new technique for realizing the domain-inversion by constant electric field rather than a pulsed one.

Reversible electrochromic effect accompanying domain-inversion in LiNbO3 : Ru : Fe crystals

A reversible electrochromic effect during the electrical poling process in LiNbO3:Ru:Fe crystals at room temperature is observed. In electrode area, both electrochromism and domain-inversion occur mutually and electrochromism is reversible during back-switch poling, which are experimentally verified, and a microstructure model to explain the mechanism is proposed. In addition, different from the undoped LiNbO3 crystals, the breakdown field (> 25.0 kV/mm) is higher than the coercive (21.0 kV/mm) measured in LiNbO3:Ru:Fe, which proves a possible new technique to realize domain-inversion by constant electric field rather than pulsed one. (c) 2005 American Institute of Physics.

敏化光波长对（Fe，Ni）：LiNbO3晶体全息记录性能的影响

分别采用514nm绿光、488nm蓝光和390nm紫外光作为敏化光，633nm红光作为记录光，详细研究了敏化光波长对氧化（Fe，Ni）：LiNbO3晶体全息记录性能的影响。结果表明：随着敏化光波长的逐渐减小，氧化（Fe，Ni）：LiNbO3晶体的非挥发全息记录性能逐渐优化，390nm紫外光是这三种敏化光中最优的敏化光。考虑敏化光的吸收，为了在双中心全息记录中获得最优的性能，应当选择合适波长的敏化光：一方面短波长敏化光能有效地敏化深中心；另一方面短波长敏化光的吸收太强（如对光折变效应无用的基质吸收），不能沿

双掺杂LiNbO3：Fe：Mn晶体局域光折变体全息光栅形成及衍射特性

将带输运模型与二维耦合波理论相结合，研究了双掺杂LiNbO3：Fe：Mn晶体中由两束有限宽度平面波干涉产生的局域光折变体全息的动力学机制及其衍射特性。采用三步法联立求解了双中心带输运物质波方程和二维耦合波方程。数值计算结果表明，局域光折变体全息光栅的空间电荷场在空间上呈不均匀分布。当光栅区域较小时空间电荷场较强，随着光栅区域的增大，空间电荷场急剧下降，并降低一个数量级。此外，在接近光束入射边界的区域，空间电荷场时空变化规律与一维无限大光折变体全息光栅的结果相似，随着光栅区域的扩大，边界效应对空间电荷场的影

Effect of wavelength of sensitizing light on holographic storage properties in LiNbO3 : Fe : Ni crystal

By sensitizing with 514 nm green light, 488 nm blue light and 390 nm ultraviolet light, respectively, recording with 633 nm red light, effect of wavelength of sensitizing light on holographic storage properties in LiNbO3:Fe:Ni crystal is investigated in detail. It is shown that by shortening the wavelength of sensitizing light gradually, nonvolatile holographic recording properties of oxidized LiNbO3:Fe:Ni crystal is optimized gradually, 390 nm ultraviolet light is the best as the sensitizing light. Considering the absorption of sensitizing light, to obtain the best performance in two-center holographic recording we must choose a sensitizing wavelength that is long enough to prevent unwanted absorptions (band-to-band, etc.) and short enough to result in efficient sensitization from the deep traps. So in practice a trade-off is always needed. Explanation is presented theoretically. (c) 2005 Elsevier GmbH. All rights reserved.

Proton-Coupled Reduction of N2 Facilitated by Molecular Fe Complexes

The activation of Fe-coordinated N₂ via the formal addition of hydrogen atom equivalents is explored in this thesis. These reactions may occur in nitrogenase enzymes during the biological conversion of N₂ to NH₃. To understand these reactions, the N₂ reactivity of a series of molecular Fe(N₂) platforms is investigated. A trigonal pyramidal, carbon-ligated Fe^I complex was prepared that displays a similar geometry to that of the resting state 'belt' Fe atoms of nitrogenase. Upon reduction, this species was shown to coordinate N₂, concomitant with significant weakening of the C-Fe interaction. This hemilability of the axial ligand may play a critical role in mediating the interconversion of Fe(N_xH_y) species during N₂ conversion to NH₃. In fact, a trigonal pyramidal borane-ligated Fe complex was shown to catalyze this transformation, generating up to 8.49 equivalents of NH₃. To shed light on the mechanistic details of this reaction, protonation of a borane-ligated Fe(N₂) complex was investigated and found to give rise to a mixture of species that contains an iron hydrazido(2-) [Fe(NNH₂)] complex. The identification of this species is suggestive of an early N-N bond cleavage event en route to NH₃ production, but the highly-reactive nature of this complex frustrated direct attempts to probe this possibility. A structurally-analogous silyl-ligated Fe(N₂) complex was found to react productively with hydrogen atom equivalents, giving rise to an isolable Fe(NNH₂) species. Spectroscopic and crystallographic studies benefited from the enhanced stability of this complex relative to the borane analogue. One-electron reduction of this species initiates a spontaneous disproportionation reaction with an iron hydrazine [Fe(NH₂NH₂)] complex as the predominant reaction product. This transformation provides support for an Fe-mediated N₂ activation mechanism that proceeds via a late N-N bond cleavage. In hopes of gaining more fundamental insight into these reactions, a series of Fe(CN) complexes were prepared and reacted with hydrogen-atom equivalents. Significant quantities of CH₄ and NH₃ are generated in these reactions as a result of complete C-N bond activation. A series of Fe(CNH_x) were found to be exceptionally stable and may be intermediates in these reactions. The stability of these compounds permitted collection of thermodynamic parameters pertinent to the unique N-H bonds. This data is comparatively discussed with the theoretically-predicted data of the N₂-derived Fe(NNH_x) species. Exceptionally-weak N-H bond enthalpies are found for many of these compounds, and sheds light on their short-lived nature and tendency to evolve H₂. As a whole, these works both establish and provide a means to understand Fe-mediated N₂ activation via the addition of hydrogen atom equivalents.

Deposición de carbono en las superficies de películas delgadas de Fe sumergidas en tolueno en condiciones ambientales

Las nanoestructuras han sido muy estudiadas debido a su importancia en aplicaciones tecnológicas y biomédicas, como por ejemplo el recubrimiento de los sensores y biosensores. Estas necesitan ser recubiertas para su protección y/o funcionalización. Un estudio sobre las superficies de nanopartículas magnéticas y esféricas (MNPs) de Fe y Ni reveló que el tolueno actúa como catalizador de reacciones de condensación de los componentes aromáticos formando estructuras gigantes, policíclicas e irregulares, creando así una especie de recubrimiento de carbono. También se ha estudiado la posibilidad de formar recubrimientos con carbono en películas de hierro y permalloy (FeNi) en tiempos largos de tratamiento de 1 año. En el presente trabajo, debido a los resultados anteriores para las películas delgadas de hierro, se ha estudiado el desarrollo del proceso de deposición del grafeno defectuoso a temperatura ambiente, sobre las superficies de las películas delgadas de hierro en periodos de entre unos días hasta medio año aproximadamente. Se ha hecho un estudio en función del tiempo de inmersión en tolueno de las propiedades estructurales y magnéticas de las películas de hierro depositadas sobre vidrio. Las películas de hierro han sido preparadas por el método de pulverización catódica y después sumergidas en tolueno. Las técnicas utilizadas para la caracterización estructural han sido, la difracción de Rayos-X, los estudios de microscopia electrónica de barrido (SEM) y la perfilómetría. La caracterización magnética se ha hecho con un magnetómetro de Kerr (MOKE) y un magnetómetro vibrante (VSM). Las muestras cristalizaban en el sistema cúbico FCC del grupo espacial Fm-3m, con parámetro de celda de 3.5922Ǻ. El tamaño de dominio coherente para los índices de Miller (110) ha ido aumentando a lo largo del tratamiento. Para el índice de Miller (211) el tamaño de dominio coherente ha disminuido. Este comportamiento se explica tendiendo en cuenta el modelo propuesto en la literatura científica del proceso de formación de las estructuras de grafeno defectuoso. El análisis de las imágenes de SEM y los correspondientes datos de la emisión de Rayos-X han confirmado la presencia del carbono en la superficie. La cantidad del carbono en la superficie de las películas de hierro aumenta con el incremento del tiempo de inmersión en tolueno. Ha sido posible detectar la presencia del carbono en la superficie después de 9 días de inmersión (por lo tanto, el proceso de las estructuras policíclicas e irregulares es relativamente rápido). La deposición del carbono no resulta en una formación de estructura uniforme, así que cuanto más largo es el tratamiento, más complicadas son las estructuras. Como resultado del tratamiento superficial durante aproximadamente medio año, se observa un aumento de rugosidad de un micrómetro aproximadamente. La diferencia entre las medidas de MOKE y VSM para el campo coercitivo y la remanencia, se explica teniendo en cuenta el proceso de oxidación de la superficie y la interacción de algunas partes de la película de hierro con el tolueno, que pueden causar la relajación de las tensiones. La imanación de saturación obtenida para las películas después del tiempo de tratamiento de 135 días es de 192 emu por gramo. La disminución de la imanación de saturación es debida a la oxidación de las películas por el contacto con la atmósfera y el tolueno. En un cálculo aproximado se ha llegado a la conclusión que dicha capa tiene un espesor de 50 nm, repartida en dos capas de 25 nm. De todo lo anterior y de la base de análisis de las propiedades estructurales y magnéticas de las películas delgadas de hierro sumergidas en tolueno para hacer el tratamiento superficial a temperatura ambiente, se concluye, que las estructuras policíclicas e irregulares de grafeno defectuoso se forman relativamente rápido. El tratamiento con el tolueno no causa muchos cambios en la estructura y en las propiedades magnéticas, se trata de procesos superficiales. La modificación in situ de películas de hierro en tolueno, puede ser candidato a método de protección y funcionalización de los sensores magnéticos.

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.

Study of near-infrared nonvolatile two-center holographic recording in LiNbO3:Fe:Rh crystal

The near-infrared nonvolatile holographic recording has been realized in a doubly doped LiNbO3:Fe:Rh crystal by the traditional two-center holographic recording scheme, for the first time. The recording performance of this crystal has been investigated by recording with 633 nm red light, 752 nm red light and 799 nm near-infrared light and sensitizing with 405 nm purple light. The experimental results show that, co-doped with Fe and Rh, the near-infrared absorption and the photovoltaic coefficient of shallow trap Fe are enhanced in this LiNbO3:Fe:Rh crystal, compared with other doubly doped LiNbO3 crystals Such as LiNbO3:Fe:Mn. It is also found that the sensitizing light intensity affects the near-infrared recording sensitivity in a different way than two-center holographic recording with shorter wavelength, and the origin of experimental results is analyzed. (C) 2007 Elsevier GrnbH. All rights reserved.

Valorization of scrap tires pyrolysis oil (STPO) through a 2-stage hydrotreating-hydrocracking strategy. Process variables and kinetic modeling

232 p.