Cheng Kwok Kei = 高分子電解質-膠體複合體系的相互作用和極化率 / 鄭國基. / Thesis submitted in: November 2004. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2005. / Includes bibliographical references (leaves 68-73). / Text in English; abstracts in English and Chinese. / Cheng Kwok Kei = Gao fen zi dian jie zhi-jiao ti fu he ti xi de xiang hu zuo yong he ji hua lü / Zheng Guoji. / Chapter 1 --- Introduction --- p.1 / Chapter 1.1 --- Polyelectrolyte Colloid Complex --- p.1 / Chapter 1.2 --- Image charges --- p.3 / Chapter 1.3 --- Objective of the thesis --- p.3 / Chapter 2 --- Equations for induced image charges (Review) --- p.5 / Chapter 2.1 --- Introduction --- p.5 / Chapter 2.2 --- Image effect --- p.6 / Chapter 2.2.1 --- The potential --- p.6 / Chapter 2.2.2 --- Surface charge density --- p.8 / Chapter 2.2.3 --- Potential energy --- p.9 / Chapter 3 --- Polarizability of a polyelectrolyte colloid complex --- p.11 / Chapter 3.1 --- Introduction --- p.11 / Chapter 3.2 --- The Simulation Model --- p.12 / Chapter 3.2.1 --- Energy of the Complex --- p.13 / Chapter 3.2.2 --- Dipole of the Complex --- p.15 / Chapter 3.2.3 --- Thermal Energy --- p.18 / Chapter 3.3 --- Calculating Method --- p.18 / Chapter 3.3.1 --- Monte Carlo Simulation --- p.19 / Chapter 3.3.2 --- Partition Function Calculation --- p.20 / Chapter 3.4 --- Polarizability --- p.22 / Chapter 3.4.1 --- Compare polarizability of the complex with a permanent dipole --- p.22 / Chapter 3.4.2 --- Results and Discussion --- p.23 / Chapter 3.5 --- Effect of image charges for the complex --- p.33 / Chapter 3.6 --- Conclusion --- p.37 / Chapter 4 --- Correlation and Interaction of complexes - without induced charges --- p.38 / Chapter 4.1 --- Introduction --- p.38 / Chapter 4.2 --- The Simulation Model --- p.39 / Chapter 4.2.1 --- Energy of the system --- p.40 / Chapter 4.2.2 --- Dipole Moment --- p.42 / Chapter 4.3 --- Results and Discussion --- p.43 / Chapter 4.3.1 --- Polarizability of complex --- p.43 / Chapter 4.3.2 --- Correlations between two complexes --- p.46 / Chapter 4.3.3 --- Potential of mean force --- p.50 / Chapter 4.4 --- Conclusion --- p.52 / Chapter 5 --- Correlation between Two Complexes - with induced charges --- p.53 / Chapter 5.1 --- Introduction --- p.53 / Chapter 5.2 --- Induced Surface Charges --- p.54 / Chapter 5.2.1 --- Surface charges --- p.54 / Chapter 5.2.2 --- Energy of system --- p.55 / Chapter 5.2.3 --- Dipole Moment --- p.57 / Chapter 5.3 --- Results and Discussion --- p.58 / Chapter 5.3.1 --- Polarizability of complexes --- p.59 / Chapter 5.3.2 --- Correlation between two complexes --- p.61 / Chapter 5.3.3 --- Potential of mean force --- p.63 / Chapter 5.4 --- Conclusion --- p.64 / Chapter 6 --- Summary --- p.66 / Bibliography --- p.68 / Chapter A --- Mathematical calculation of the dipole moment of a complex --- p.74 / Chapter A.1 --- Equation of mean squared dipole --- p.74 / Chapter A.2 --- z-component of dipole and squared dipole --- p.76

Atomic polarizability plays an essential role in topics ranging from van der Waals interactions, state lifetimes, and indices of refraction, to next generation atomic clocks and atomic parity non-conservation experiments. Polarizability measurements, such as the ones described in this thesis, provide valuable input to these subjects and serve as benchmark tests for sophisticated atomic structure calculations. We measured the static polarizability of potassium and rubidium with record precision and 0.5% uncertainty using a Mach-Zehnder atom interferometer with an electric-field gradient. To support future precision measurements of polarizability, we developed a new atom beam velocity measurement technique called phase choppers. Using phase choppers, we demonstrated measurements of mean atom beam velocity with an uncertainty of 0.1%. We also developed a new way to probe atomic structure: a measurement of a zero-crossing of the dynamic polarizability of potassium, known as a magic-zero wavelength. We measured the first magic-zero wavelength of potassium with 1.5 pm uncertainty and established a new benchmark measurement for the ratio of the D1 and D2 line strengths. Finally, we propose the use of a resonant photoionization detector for measurements of strontium polarizability, and the use of contrast interferometry for measurements of alkali dimer tensor polarizabilities.

Understanding organic semiconductor interfaces is critical to developing organic photovoltaics (OPV). OPV interfaces are disordered due to weak intermolecular interactions, resulting in diverse charge transfer micro-environments. I present experimental data isolating high-order intermolecular interactions controlling interfacial energy level alignment and describe new instrumental capabilities providing access to the local electronic and kinetic landscape at organic semiconductor interfaces. Interface formation between vanadyl naphthalocyanine (VONc) and highly ordered pyrolytic graphite (HOPG) is investigated. Ultraviolet photoemission spectroscopy (UPS) shows that the VONc binding energy (BE) decouples from the work function, shifting in an opposite direction and contradicting the standard interface dipole model. This effect is quantitatively described using an electrostatic depolarization model and confirmed by simulations which show an inhomogeneous potential at the interface. New data and literature values suggest orthogonality between polarizability and molecular dipole in polar porphyrazines. Their potential for interface engineering is discussed. The electron-rich Au(111)/VONc interface is investigated. The organic layer induces a large interface dipole in Au(111) which can be fit to a depolarization model. Ionization potential and depolarization data suggest that the second VONc layer on Au(111) adopts a tilted geometry. Electrostatic differences between Au(111)/VONc and HOPG/VONc are discussed, demonstrating that interface dipole contributions are not interchangeable. The surface states of the Au(111)/VONc interface are characterized by angle resolved 2-photon photoemission to determine the magnitude of the perturbation. The measured free-electron-like effective mass and BE destabilization of the Shockley state is attributed to step edges caused by lifting the Au(111) (22 x √3) reconstruction. The Shockley state is accessible primarily through resonance with the n = 1 image state. Another resonance between the image state and a molecular state of VONc is tentatively identified. Design and construction of a confocal fluorescence microscope capable of single molecule detection in ultrahigh vacuum is described. Initial images and fluorescence trajectories demonstrate the ability to measure charge transfer kinetics between an individual organic semiconductor molecule and well-characterized insulating surfaces. Progress towards completion of a scanning photoionization microscope is presented. The microscope demonstrates diffraction-limited imaging capabilities using fs-laser-generated photoelectron current as contrast. Recommendations are given towards achieving spectral resolution and for future experimental systems.

Thesis (M.Sc.)--Memorial University of Newfoundland, 2004. / Bibliography: leaves 102-112.

The following abstract is for a thesis submitted to the University of Manchester for the degree of Doctor in Philosophy by Omar AbdelRehim AbdelKerim in 2015.Anti-personnel (AP) mines remain a global problem that affects communities around the world, with 110 million active landmines still present. Landmines are a particularly callous and indiscriminate type of weapon detonating irrespective of presence of an enemy soldier or a child. Their devastating effect on communities has led to their ban through the 1997 Mine Ban Treaty. Current detectors used for mine clearance operations have an impeding weakness that has prompted this research; metal detectors used in humanitarian demining suffer from a high False Alarm Rate (FAR) prompting regular excavation of metallic clutter. The research presented aims to develop a detector capable of discriminating between metallic clutter and mines through the use of the magnetic polarizability dyadic tensor to reduce FARs, increase demining efficiency and improve deminer’s safety. A measurement apparatus was designed and constructed to perform spectroscopic magnetic measurements of small symmetrical metallic objects and produce for the first time unscaled accurate tensor values. The tensors deduced from the measurements were validated against analytical and simulated results and were found to be within 5% of measured tensors. The tensors of minimum metal AP mine surrogates and metallic clutter of symmetrical shape were measured and formed part of a tensor library to be used later by future research. This is in addition to a set of un-circulated US coinage which could be used as a calibration metric and a comparison piece for future work in this area. A detailed description of the coil design and manufacturing process is presented to develop a coil array capable of inverting buried metallic object tensors. The selection criterion was poised to identify an array that was best suited to perform the correct measurements in order to invert to an accurate tensor. The manufactured coil exhibited strong mutual coupling between the receive coils deeming it unfit for the portable detector; however, the findings of the work presented and the selection criterion developed has aided the future design of a suitable coil array. Expected signal levels from minimum metal mine detection were calculated and helped aide in the design of future detectors to ensure suitable SNR performance is achieved. A portable detector has been developed using the sensor head presented within this thesis. Work still lies ahead to achieve the complete detector capable of performing target characterisation and clutter elimination; however, significant advances have been made and are presented throughout this thesis.

Neste trabalho apresentamos alguns estudos teóricos sobre propriedades eletrônicas de sistemas atômicos e moleculares em fase líquida e ambiente supercrítico. A utilização dos fluidos supercríticos têm atraído muito interesse como meio solvente para propriedades moleculares, reações químicas e são vistos como alternativa aos solventes orgânicos t´óxidos. Assim como nos solventes convencionais, descrever suas propriedades por meio de estudos em n´nível molecular tem se tornado tão interessante quanto seu uso prático. Primeiramente realizamos o estudo da polarizabilidade estática do argônio e como esta propriedade se comporta em função da variação de pressão. Fizemos também um estudo deste sistema em torno do ponto crítico e região supercrítica. Dentro do intervalo de pressão que estudamos, não observamos variações significativas na polarizabilidade, embora no regime de baixas densidades este sistema apresentou certa dependência da polarizabilidade com a densidade. Neste estudo, também calculamos a constante dielétrica no ponto crítico. Em seguida estudamos o espectro de absorção do ´átomo de xenônio em ambiente formado por argônio líquido. Nesta parte, realizamos várias simulações com o objetivo de verificar o deslocamento da linha de absorção 5p 6s deste ´átomo em relação `a densidade, explorando também as condições supercríticas. Observamos que o deslocamento do espectro ocorrido em meio solvente é para maiores energias (blue shift) `a medida que a densidade aumenta, e obtemos bom acordo com os valores medidos. Por ultimo, realizamos um estudo da mudança de um espectro eletrônico molecular onde o solvente é a ´agua supercrítica. Utilizamos a molécula paranitroanilina como sonda solvatocromica, e observamos que mesmo no regime de alta temperatura e baixa densidade ainda ocorre a formação de ligações de hidrogênio entre soluto e solvente. Obtemos um red shift para a transição eletrônica em agua supercrítica. Este resultado é medido experimentalmente tanto para ´agua em condições ambiente como em condição supercrítica, mas em ´agua supercrítica o deslocamento ´e menor. Nosso resultado para a agua supercrítica está em bom acordo com o resultado experimental e mostra que a maior contribuição para este deslocamento ´e devido ao efeito das interações eletrostáticas. Porém, ao compararmos os resultados da ´agua em condições supercríticas com as condições normais de temperatura e pressão e o dióxido de carbono supercrítico como solventes, os resultados indicam que a aproximação de incluir apenas interações eletrostáticas ´e menos satisfatória e fornece somente parte do efeito de solvente. / In this work we present some theoretical studies of the electronic properties of atomic and molecular systems in liquid and supercritical environments. The study of supercritical fluids is a interesting topic in solvent effects on molecular properties and chemical reactions. Their use can be an alternative to organic toxic solvents. Describing their molecular solvent properties, as opposite to conventional solvents, has become important as of pratical use. First we study the static polarizability of atomic argon and its behavior with pressure. The critical and near critical points also were considered in this study. In the range of pressures used, it is not observed significant changes in the polarizability, although the system present some dependence with density in the supercritical region. We have then determined the dielectric constant at the critical point. Next we study the absorption electronic spectra of xenon atom in liquid argon environment. In this part, we performed several simulations with the aim of verifying the density dependence of the spectral shift of the 5p 6s line of xenon. The supercritical region was also explored. We obtain the spectral blue shift in solvent environment for increasing density in good agreement with experiments. Finally, we study the electronic spectra of a solvatochromic probe molecule, the paranitroaniline, in supercritical water and supercritical carbon dioxide. We observe that even for high temperature hydrogen bond persists between the solute and the water molecules. A red shift in the transition of the electronic spectra of paranitroaniline is well described. This red shift is observed experimentally in water, but in supercritical water it is less pronounced. Our results for supercritical water is in good agreement with the experimental result and show that the long-range electrostatic contribution dominates the solute-solvente interaction and gives the largest influence in the calculated spectrum. Water in normal conditions and supercritical carbon dioxide were also considered for comparison and the results indicates that including only the electrostatic contribution is less satisfactory and gives only part of the total solvent effect.

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第19240号 / 工博第4075号 / 新制||工||1628(附属図書館) / 32239 / 京都大学大学院工学研究科化学工学専攻 / (主査)教授 山本 量一, 教授 宮原 稔, 教授 松坂 修二 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM

Filtration processes, whether on the microfluidic, clinical treatment systems, or industrial scale (e.g., point-of-care diagnostics, dialysis, and biopharmaceutical manufacturing, respectively), are often inseparable from membrane clogging (fouling). As a consequence, most, if not all, filtration systems require frequent maintenance to maintain functionality and efficiency. The thesis of this project hypothesizes that Dielectrophoresis can be combined with standard filtration to reduce filter fouling, extending membrane life, and enabling continuous operation. This project investigates a method to reduce fouling, add specificity and efficiency, and decrease the cost and challenge of filtration based biofluid separations. To substantiate this thesis, we designed, fabricated, and tested a filtration system to filter micron diameter particles in suspension using Millipore™ membranes together with fabricated electrodes in a cross-flow filtration system. This prototype device elicits a repulsive dielectrophoretic (DEP) force via the application of a direct current (5-20 volts) sourced from a computer controlled voltage sequencer, designed to levitate and remove larger particles (> 6 µm) before particulate-membrane interaction. Analysis of the results shows a sufficient decrease in particles adhered to the filtration membrane, as compared to control, suggesting DC DEP may be a valid effector in this device. We are convinced that further research will augment the results validating the proof-of-concept thesis presented herein.

One of the most promising methods for surmounting the high-degree polynomial scaling wall associated with electron correlating wave function methods is the local correlation technique of Pulay and Saebø. They have proposed using a set of localized occupied and virtual orbitals free of the canonical constraint commonly employed in quantum chemistry, resulting in a method that scales linearly (in the asymptotic limit) with molecular size. Pulay and Saeb$oslash; first applied their methods to configuration interaction and later to M$oslash;ller-Plesset perturbation theory. Werner et al. have have extended the local correlation scheme of Pulay and Saeb$oslash; to coupled-cluster theory. One of the pitfalls of the local correlation methods developed by Pulay and Saeb$oslash; is the dependence of domain selection on the molecular geometry. In other words, as the geometry changes the domain structure of the local correlation calculation can change also, leading to discontinuities in the potential energy surface. We have examined the size of these discontinuities for the homolytic bond cleavage of fluoromethane and the heterolytic bond dissociation of singlet ketene and propadienone. Properties such as polarizabilities and optical rotation are realized through linear response theory, where the Hamiltonian is subject to an external perturbation and the wave function is allowed to respond to the applied perturbation. Within the context of local correlation it is necessary to understand how the domain structure alters in response to an applied perturbation. We have proposed using solutions to the CPHF equations (coupled-perturbed Hartree-Fock) in order to predict the correlation response to an applied perturbation. We have applied this technique to the calculation of polarizabilities, with very favorable results, and also to optical rotation, with mixed results. / Ph. D.

Berry curvature appears in the semi-classical theory of Bloch electrons already to first order in electromagnetic fields, resulting in profound modification of the carrier velocity and phase space density of states. Here we derive the equations of motion for the physical position and crystal momentum to second order in the fields. The dynamics still has a Hamiltonian structure, albeit with noncanonical Poisson brackets between the physical variables. We are able to expand both the carrier energy and the Poisson brackets to second order in the fields with terms of clear physical meaning. To demonstrate the utility of our theory, we obtain with much ease the electromagnetic response and orbital magnetic susceptibility. / text