Nature of the radical intermediates in a substituted cyclopropylcarbiny-allylcarbinyl system

We have sought to determine the nature of the free-radical precursors to ring-opened hydrocarbon 5 and ring-closed hydrocarbon 6. Reasonable alternative formulations involve the postulation of hydrogen abstraction (a) by a pair of rapidly equilibrating classical radicals (the ring-opened allylcarbinyl-type radical 3 and the ring-closed cyclopropylcarbinyl-type 4), or (b) by a nonclassical radical such as homoallylic radical 7.

[Figure not reproduced.]

Entry to the radical system is gained via degassed thermal decomposition of peresters having the ring-opened and the ring-closed structures. The ratio of 6:5 is essentially independent of the hydrogen donor concentration for decomposition of the former at 125° in the presence of triethyltin hydrdride. A deuterium labeling study showed that the α and β methylene groups in 3 (or the equivalent) are rapidly interchanged under these conditions.

Existence of two (or more) product-forming intermediates is indicated (a) by dependence of the ratio 6:5 on the tin hydride concentration for decomposition of the ring-closed perester at 10 and 35°, and (b) by formation of cage products having largely or wholly the structure (ring-opened or ring-closed) of the starting perester.

Relative rates of hydrogen abstraction by 3 could be inferred by comparison of ratios of rate constants for hydrogen abstraction and ortho-ring cyclization:

[Figure not reproduced.]

At 100° values of k_a/k_r are 0.14 for hydrogen abstraction from 1,4-cyclohexadiene and 7 for abstraction from triethyltin hydride. The ratio 6:5 at the same temperature is ~0.0035 for hydrogen abstraction from 1,4-cyclohexadiene, ~0.078 for abstraction from the tin hydride, and ≥ 5 for abstraction from cyclohexadienyl radicals. These data indicate that abstraction of hydrogen from triethyltin hydride is more rapid than from 1,4-cyclohexadiene by a factor of ~1000 for 4, but only ~50 for 3.

Measurements of product ratios at several temperatures allowed the construction of an approximate energy-level scheme. A major inference is that isomerization of 3 to 4 is exothermic by 8 ± 3 kcal/mole, in good agreement with expectations based on bond dissociation energies. Absolute rate-constant estimates are also given.

The results are nicely compatible with a classical-radical mechanism, but attempted interpretation in terms of a nonclassical radical precursor of product ratios formed even from equilibrated radical intermediates leads, it is argued, to serious difficulties.

The roles played by hydrogen abstraction from 1,4,-cyclohexadiene and from the derived cyclohexadienyl radicals were probed by fitting observed ratios of 6:5 and 5:10 in the sense of least-squares to expressions derived for a complex mechanistic scheme. Some 30 to 40 measurements on each product ratio, obtained under a variety of experimental conditions, could be fit with an average deviation of ~6%. Significant systematic deviations were found, but these could largely be redressed by assuming (a) that the rate constant for reaction of 4 with cyclohexadienyl radical is inversely proportional to the viscosity of the medium (i.e., is diffusion-controlled), and (b) that k_a/k_r for hydrogen abstraction from 1,4-cyclohexadiene depends slightly on the composition of the medium. An average deviation of 4.4% was thereby attained.

Degassed thermal decomposition of the ring-opened perester in the presence of the triethyltin hydride occurs primarily by attack on perester of triethyltin radicals, presumably at the –O-O- bond, even at 0.01 M tin hydride at 100 and 125°. Tin ester and tin ether are apparently formed in closely similar amounts under these conditions, but the tin ester predominates at room temperature in the companion air-induced decomposition, indicating that attack on perester to give the tin ether requires an activation energy approximately 5 kcal/mole in excess of that for the formation of tin ester.

Energy transfer in molecular collisions

Two general, numerically exact, quantum mechanical methods have been developed for the calculation of energy transfer in molecular collisions. The methods do not treat electronic transitions because of the exchange symmetry of the electrons. All interactions between the atoms in the system are written as potential energies.

The first method is a matrix generalization of the invariant imbedding procedure, ^{17, 20} adapted for multi-channel collision processes. The second method is based on a direct integration of the matrix Schrödinger equation, with a re-orthogonalization transform applied during the integration.

Both methods have been applied to a collinear collision model for two diatoms, interacting via a repulsive exponential potential. Two major studies were performed. The first was to determine the energy dependence of the transition probabilities for an H₂ on the H₂ model system. Transitions are possible between translational energy and vibrational energy, and from vibrational modes of one H₂ to the other H₂. The second study was to determine the variation of vibrational energy transfer probability with differences in natural frequency of two diatoms similar to N₂.

Comparisons were made to previous approximate analytical solutions of this same problem. For translational to vibrational energy transfer, the previous approximations were not adequate. For vibrational to vibrational energy transfer of one vibrational quantum, the approximations were quite good.

Determination of electronic energy levels of molecules by 90° low energy electron scattering

A review of the theory of electron scattering indicates that low incident beam energies and large scattering angles are the favorable conditions for the observation of optically forbidden transitions in atoms and molecules.

An apparatus capable of yielding electron impact spectra at 90° with incident electron beam energies between 30 and 50 electron volts is described. The resolution of the instrument is about 1 electron volt.

Impact spectra of thirteen molecules have been obtained. Known forbidden transitions to the helium 2³S, the hydrogen b³Ʃ⁺_u, the nitrogen A³Ʃ⁺_u, B³π_g, a’π_g, and C³π_u, the carbon monoxide a³π, the ethylene ᾶ³B_1u, and the benzene ᾶ³B_1u states from the corresponding ground states have been observed.

In addition, singlet-triplet vertical transitions in acetylene, propyne, propadiene, norbornadiene and quadricyclene, peaking at 5.9, 5.9, 4.5, 3.8, and 4.0 ev (±0.2 ev), respectively, have been observed and assigned for the first time.

The binding and catalytic properties of lysozyme

The binding and catalytic properties of hen's egg white lysozyme have been studied by a variety of techniques. These studies show that the enzyme has three contiguous binding subsites, A, B, and C. The application of nuclear magnetic resonance (NMR) spectroscopy to probe the binding environment of several saccharides to lysozyme has demonstrated that the reducing end sugar rings of chitotriose, chitobiose and the β-form of N-acetylglucosamine all bind in subsite C. The central sugar ring of chitotriose and the sugar ring at the nonreducing end of chitobiose were found to bind in subsite B, while the nonreducing end sugar residue of chitotriose occupied subsite A. The dynamics of the binding process has also been investigated by NMR. The formation rate constant of chitobiose--and chitotriose-enzyme complexes were found to be about 4 X 10^-6 M^-1 sec^-1 with small activation energies.

The stereochemical path of the lysozyme catalyzed hydrolysis of glycosidic bonds has been shown to proceed with at least 99.7% retention of configuration at C-1 of the sugar. The lysozyme catalyzed hydrolysis of glucosidic bonds has been shown to be largely carbonium ion in character by virtue of the α-deuterium kinetic isotope effect (k_H/k_D = 1.11) observed for the reaction. It is probable that the mechanism of action of the enzyme involves a carbonium ion intermediate which is stereospecifically quenched by solvent. However, acetamido group participation cannot be ruled out for natural substrates.

I. Non-linear effects in a self-consistent calculation of SU_3 symmetry breaking in strong interaction coupling constants. II. Direct-channel reggeization of strong interaction scattering amplitudes

The thesis is divided into two parts. Part I generalizes a self-consistent calculation of residue shifts from SU₃ symmetry, originally performed by Dashen, Dothan, Frautschi, and Sharp, to include the effects of non-linear terms. Residue factorizability is used to transform an overdetermined set of equations into a variational problem, which is designed to take advantage of the redundancy of the mathematical system. The solution of this problem automatically satisfies the requirement of factorizability and comes close to satisfying all the original equations.

Part II investigates some consequences of direct channel Regge poles and treats the problem of relating Reggeized partial wave expansions made in different reaction channels. An analytic method is introduced which can be used to determine the crossed-channel discontinuity for a large class of direct-channel Regge representations, and this method is applied to some specific representations.

It is demonstrated that the multi-sheeted analytic structure of the Regge trajectory function can be used to resolve apparent difficulties arising from infinitely rising Regge trajectories. Also discussed are the implications of large collections of "daughter trajectories."

Two things are of particular interest: first, the threshold behavior in direct and crossed channels; second, the potentialities of Reggeized representations for us in self-consistent calculations. A new representation is introduced which surpasses previous formulations in these two areas, automatically satisfying direct-channel threshold constraints while being capable of reproducing a reasonable crossed channel discontinuity. A scalar model is investigated for low energies, and a relation is obtained between the mass of the lowest bound state and the slope of the Regge trajectory.

Beta and gamma vibrational bands in deformed nuclei

Energies and relative intensities of gamma transitions in ¹⁵²Sm, ¹⁵²Gd, ¹⁵⁴Gd, ¹⁶⁶Er, and ²³²U following radioactive decay have been measured with a Ge(Li) spectrometer. A peak fitting program has been developed to determine gamma ray energies and relative intensities with precision sufficient to give a meaningful test of nuclear models. Several previously unobserved gamma rays were placed in the nuclear level schemes. Particular attention has been paid to transitions from the beta and gamma vibrational bands, since the gamma ray branching ratios are sensitive tests of configuration mixing in the nuclear levels. As the reduced branching ratios depend on the multipolarity of the gamma transitions, experiments were performed to measure multipole mixing ratios for transitions from the gamma vibrational band. In ¹⁵⁴Gd, angular correlation experiments showed that transitions from the gamma band to the ground state band were predominantly electric quadrupole, in agreement with the rotational model. In ²³²U, the internal conversion spectrum has been studied with a Si(Li) spectrometer constructed for electron spectroscopy. The strength of electric monopole transitions and the multipolarity of some gamma transitions have been determined from the measured relative electron intensities.

The results of the experiments have been compared with the rotational model and several microscopic models. Relative B(E2) strengths for transitions from the gamma band in ²³²U and ¹⁶⁶Er are in good agreement with a single parameter band mixing model, with values of z₂= 0.025(10) and 0.046(2), respectively. Neither the beta nor the gamma band transition strengths in ¹⁵²Sm and ¹⁵⁴Gd can be accounted for by a single parameter theory, nor can agreement be found by considering the large mixing found between the beta and gamma bands. The relative B(E2) strength for transitions from the gamma band to the beta band in ²³²U is found to be five times greater than the strength to the ground state band, indicating collective transitions with strength approximately 15 single particle units.

Solar flare particle propagation--comparison of a new analytic solution with spacecraft measurements

A new analytic solution has been obtained to the complete Fokker-Planck equation for solar flare particle propagation including the effects of convection, energy-change, corotation, and diffusion with ĸ_r = constant and ĸ_Ɵ ∝ r². It is assumed that the particles are injected impulsively at a single point in space, and that a boundary exists beyond which the particles are free to escape. Several solar flare particle events have been observed with the Caltech Solar and Galactic Cosmic Ray Experiment aboard OGO-6. Detailed comparisons of the predictions of the new solution with these observations of 1-70 MeV protons show that the model adequately describes both the rise and decay times, indicating that ĸ_r = constant is a better description of conditions inside 1 AU than is ĸ_r ∝ r. With an outer boundary at 2.7 AU, a solar wind velocity of 400 km/sec, and a radial diffusion coefficient ĸ_r ≈ 2-8 x 10²⁰ cm²/sec, the model gives reasonable fits to the time-profile of 1-10 MeV protons from "classical" flare-associated events. It is not necessary to invoke a scatter-free region near the sun in order to reproduce the fast rise times observed for directly-connected events. The new solution also yields a time-evolution for the vector anisotropy which agrees well with previously reported observations.

In addition, the new solution predicts that, during the decay phase, a typical convex spectral feature initially at energy T_o will move to lower energies at an exponential rate given by T_KINK = T_oexp(-t/Ƭ_KINK). Assuming adiabatic deceleration and a boundary at 2.7 AU, the solution yields Ƭ_KINK ≈ 100h, which is faster than the measured ~200h time constant and slower than the adiabatic rate of ~78h at 1 AU. Two possible explanations are that the boundary is at ~5 AU or that some other energy-change process is operative.

Laser diode array side-pumped acousto-optic induced unidirectional operation Q-switched Nd : YAG slab ring laser

A laser-diode array (LDA) side-pumped Nd:YAG slab ring laser is described that incorporates a prism-shaped acousto-optic modulator to enforce unidirectional operation and Q-switching. When pumped by the maximum power of 50 W, Q-switched energies of 3.6 mJ and 50 ns duration, corresponding to a peak power of 72 kW, are obtained. (C) 1999 Society of Photo-Optical Instrumentation Engineers. [S0091-3286(99)01306-9].

增益随机散射介质中的非相干辐射

用蒙特卡罗方法仿真了增益随机散射体中的非相干辐射，观察了非相干随机激光的特性。当抽运能量超过一定阈值时，散射体的整体辐射谱突然变窄；随着抽运能量继续增大，在光滑谱背景上会出现分离尖峰；散射体内空间某位置处频率组成不是单一的；辐射谱中某单个频率的空间方向分布和位置分布比较广。增益随机散射体中产生的非相干随机激光本质上既不同于无反馈的普通放大自发辐射，又不同于相干反馈形成的常规激光。解释了非相干随机激光辐射谱上出现分离尖峰的原因，出现这种现象是由于少数光子在增益散射体中经历较多次数散射后得到了相对充分的放大。

新型AgInSbTe相变薄膜的结晶活化能研究

利用磁控溅射法制备了新型AgInSbTe相变薄膜，热处理前后的X射线衍射(XRD)表明了薄膜在热作用下从非晶态转变到晶态．通过非晶态薄膜粉末的示差扫描量热(DSC)实验测定了不同升温速率条件下的结晶峰温度，计算了粉末的摩尔结晶活化能、原子激活能和频率因子,从结晶活化能E可以判断出新型AgInSbTe相变薄膜具有较高的结晶速度，可以用于高速可擦重写相变光盘．

A Real-Time Sliding Mode Control for a Wind Energy System Based on a Doubly Fed Induction Generator

In this paper, a real time sliding mode control scheme for a variable speed wind turbine that incorporates a doubly feed induction generator is described. In this design, the so-called vector control theory is applied, in order to simplify the system electrical equations. The proposed control scheme involves a low computational cost and therefore can be implemented in real-time applications using a low cost Digital Signal Processor (DSP). The stability analysis of the proposed sliding mode controller under disturbances and parameter uncertainties is provided using the Lyapunov stability theory. A new experimental platform has been designed and constructed in order to analyze the real-time performance of the proposed controller in a real system. Finally, the experimental validation carried out in the experimental platform shows; on the one hand that the proposed controller provides high-performance dynamic characteristics, and on the other hand that this scheme is robust with respect to the uncertainties that usually appear in the real systems.

355 nm脉冲激光诱导等离子体开关削波

利用激光诱导等离子体开关技术,对355 nm脉冲激光自削波进行了实验和理论研究。分别采用5种不同焦距的透镜,集中讨论了透镜焦距及激光器输出单脉冲能量对脉宽压缩的影响,发现采用焦距为200 mm的透镜能够获得最佳的脉冲压缩效果。在聚焦透镜焦距200 mm,单脉冲能量160 mJ时,获得最短脉宽3.47 ns；在激光电离Cu小孔内壁表面及空气击穿共同作用下,获得了脉宽最短达2.11 ns的脉冲激光输出。此外,根据实验结果得到了355 nm激光空气击穿阈值,并与理论估算值进行比较,两者结果较为一致。

脉冲激光晶化非晶硅薄膜的有限差分模拟

根据热传导原理，建立了脉冲激光晶化非晶硅薄膜的理论模型。运用有限差分方法研究了不同激光波长、能量密度等因素对薄膜温度变化及相变过程的影响。计算了不同波长激光器对厚度500nm非晶硅晶化的阈值能量密度。结果发现，准分子晶化的阈值能量密度最低，但是在同样的能量密度下，熔融深度却不及使用更长波长的激光器。计算并分析了升高衬底温度对结晶速度和晶粒尺寸的影响，模拟结果较好地验证了实验结论和规律。

Análisis de las diferentes tecnologías de centrales termosolares.

[ES]En este proyecto se recoge un análisis de las diferentes tecnologías de centrales termosolares. Las energías renovables tienen un papel fundamental en el abastecimiento energético futuro, ya que son una fuente inagotable con un impacto medioambiental mínimo. Dentro de las renovables, la energía termosolar es una de las más destacables en España, que se ha situado como el país líder en termosolar. Existen cuatro tecnologías diferentes para este tipo de centrales, por lo que el objetivo de este trabajo es profundizar en su conocimiento y proporcionar un criterio objetivo que permita seleccionar la más adecuada en futuras instalaciones. Para ello, se considerarán tanto aspectos técnicos como económicos, con el fin de estudiar las principales ventajas y desventajas de cada tipo.

Gestión Energética. Estimación de necesidades de potencia eólica.

[ES]Este trabajo de fin de grado (TFG) pretende analizar la evolución de la demanda en el sistema eléctrico peninsular y la potencia disponible para decidir si, en el medio plazo, será necesario incorporar nueva potencia o prescindir de alguna de las centrales existentes. El estudio considerará tanto fuentes de energía renovables como no renovables, centrándose en la necesidad, o no, de incorporar nueva potencia eólica. El TFG considerará los siguientes aspectos: el contexto energético de la península española, el análisis de la situación actual y previsiones. Este TFG responde a la necesidad de realizar una buena gestión energética con el objetivo reducir las emisiones de CO2 mejorando el uso de la energía eólica y optimizando el mix energético.