The work described in this thesis is concerned with the study of ph-ysisorbed phases by x-ray diffraction using a conventional sealed x-ray tube source. Diffraction data has been collected for a number of adsorption systems using graphite, a montmorillonite clay (Gel White) and zeolite rho as the substrate. It is well known that phases of unique two-dimensional character can be formed on the surface of graphite, and the structure of adsorbed benzene and hexaflurobenzene on graphite have been studied in this thesis. Contrary to current theoretical predictions the >/7x T/7R19" commensurate structure of submonolayer benzene has been confirmed. Submonolayer hexaflurobenzene appears to form a striped domain structure based upon the commensurate x3 lattice in which the molecules are incommensurate with the surface. ' In contrast to the homogeneous surface of graphite, the surface of a clay is microporous and heterogenous, and this gives rise to broad diffraction lines from an adsorbed phase. Despite this, the surface area of Gel White has been deduced from the evolution of the diffraction pattern of a krypton adlayer as a function of krypton loading. The formation of bulk krypton is readily identified and the small size of the three-dimensional crystallites suggests that they are formed within the micropores of the clay. The structure of adlayers of krypton and xenon within the interlayer spacing of Al-pillared Gel White has been studied in order to determine the mean inter-pillar separation. At all the coverages studied, xenon forms a close packed single layer structure whilst krypton appears to form a more complex bilayer phase. A tentative suggestion as to the mean pillar separation from this work is 30X. The adsorption site of krypton, xenon and CH3CI within zeolite rho has been determined using the method of x-ray Rietveld whole profile refinement. The principal site of adsorbed krypton and xenon is at the centre of the octagonal prism. The chlorine atom of CH3CI sits in the centre of the face of the octagonal prism and the methyl group is slightly displaced from the centre of the prism. 37-5354 Hydrodynamics of liquid encapsulation czochralski crystal growth Hicks, T.W. Bristol Ph.D. 1989 Dig. Certain aspects of crystal growth from a melt are investigated. We begin by describing the methods of producing single crystals. Particular emphasis is placed on the need for a better understanding of the hydrodynamics of the encapsulant region of the Liquid Encapsulation Czochralski (LEG) technique. We also introduce the basic physical processes which govern crystal growth. In Chapter 2 we develop a mathematical model of the encapsulant region of the LEC crystal growth system. The equations and boundary conditions that govern the encapsulant flow are formed using a vorticity-stream-function approach, after which the problem is recast in a dimensionless form. In Chapter 3 the equations of motion are represented in a finite difference form and a numerical method for solving the time-marching problem presented by the parabolic equations is developed. The elliptic stream-function equation is solved at each time level using the successive over-relaxation technique. Solutions of the model equations for the growth of GaAs crystals through B3O3 encapsulant are presented in Chapter 4. In all cases considered the flow field tends towards a steady state. For shallow encapsulants, the heat transfer in the encapsulant is conduction dominated, but for deeper encapsulants, advective heat transfer can be significant. In the last chapter we investigate the effect of Soret diffusion on the morphological stability of a freezing interface using linear stability theory. A Soret flux directed towards the interface has a destabilising effect. Over-stable modes of instability exist for very low crystal growth rates, but we are unable to find conditions under which the overstable mode is the most unstable.

Three alkyldihydrochlorosilanes were synthesized; ethyldihydrochlorosilane, octyldihydrochlorosilane and octadecyldihydrosilane. Ethyldihydrochlorosilane was produced by the reaction of ethylsilane with mercuric chloride and the other two chlorosilanes were produced by the reaction of the alkyl Grignard reagent with dichlorosilane. Each alkyldihydrochlorosilane was reacted with porous silica in an attempt to discover the extent of reaction or the highest surface concentration of bonded groups attainable. The reaction between these alkydihydrochlorosilanes and porous silica was compared to the reaction between silica and the analogous alkyldimethylchlorosilane. The rate of reaction of both type of chlorosilane was found to be essentially the same. The maximum surface concentration of bonded surface groups attainable by alkyldihydrochlorosilanes was found to be approximately 1.3 #moles/m² greater than that attainable by alkyldimethylchlorosilanes. This increased surface coverage seemed to depend very little on the chain length of the alkyl group and was attributed to the decrease in steric hindrance of the bonding silicon atom of the silane. Surface bound silyl hydrides could be oxidized selectively and sequentially to form silane silanols. Surface silanes also appeared to reduce chloroplatinic acid, but were not observed to add efficiently to olefins. The chromatographic properties of silica modified with alkyldihydrochlorosilanes were compared to those of equivalent silicas modified with alkyldimethylchlorosilanes and alkyltrichlorosilanes before and after the surface silanes were oxidized. Both normal and reversed-phase liquid chromatographic studies were conducted. In general, it was found that alkyldihydrochlorosilanes yielded the most polar modified silicas. This greater surface polarity was attributed to an increase in the activity of water in the near surface region of the bonded phase.

The growing technological application of metallic lithium has produced a greater need to understand its fundamental surface chemical properties. The use of lithium as an anode in high-energy density battery systems represents one application where this knowledge is required to optimize system performance. The surface chemistry of lithium will be discussed in terms of oxidants which represent the reductive half-cell components of these batteries, contaminants present during cell fabrication, and solvents used as the electrolytic medium. These systems have been studied in the low pressure limit ( < 1 millitorr) at atomically clean lithium surfaces using X-ray Photoelectron Spectroscopy (XPS). The lithium/sulfur dioxide system has been singled out for detailed study in order to explore the relationship between gas-phase and solution-phase processes. Electrochemical characterization of the lithium anode has been conducted as a function of controlled surface composition within this system. The ability of lithium to induce corrosion at structural components of these batteries (i.e., glass insulators) has also been investigated. A description of the chemical activity of lithium and its consequence has been developed from these results.

Significant advances in the understanding of chemical interactions at the solid-liquid interface have been made in this research through the use of diagnostic separations as a surface analysis technique. Diagnostic liquid chromatography has been employed in a detailed investigation of the thermodynamic and kinetic quantities which describe the interactions associated with a temperature induced conformational change in the octadecyldimethylsilane moieties of two different bonded silica materials. As a result of this study the nature of the structure and interactions of the ∼20Å thick interfacial region which acts as the stationary phase in reversed-phase liquid chromatography (RPLC) has been elucidated. The location and orientation of the average intermolecular interactions in the solvated layer stationary phase for solutes of differing hydrogen bonding ability and geometry has been determined as affected by bonded surface coverage, solvent hydrogen bonding competition and the structure of the solvated layer. These refinements in the model of the stationary phase solvated layer provide a much more detailed and accurate description of the intermolecular interactions responsible for retention and selectivity in RPLC than was previously available. A new modification of the method of measuring column mobile phase volume in RPLC employing retention linearization of an homologous series of compounds has been described from fundamental themodynamic principles and a statistically valid data reduction approach. The added advantage of providing thermodynamic information about the chromatographic system under study is inherent in this new technique. The experimental and theoretical bases for the new separation technique of magnetic field-flow fractionation (magnetic FFF) have been demonstrated. It has been shown that FFF techniques can be used in a diagnostic mode to study the dynamic stability of particle suspensions. The application of an external magnetic field to non-aqueous suspensions of sub-micron sized γFe₂O₃ particles, whose surface character has been modified by the adsorption of water, has been shown to enhance the suspension stability with respect to sedimentation. With the choice of proper operational conditions, magnetic FFF has also been demonstrated to be useful in monitoring particle flocculation as a result of its ability to separate particle flocculates on the basis of size.

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We quantified the chemical species present at polycrystalline cesium tin bromide perovskite, CsSnBr3 and cesium titanium bromide antifluorite, Cs2TiBr6. For CsSnBr3, experiments utilized the orthogonal reactivity of the Cs+ cation, the Sn2+ cation, and the Br– halide anion. Ambient- pressure exposure to BF3 solutions probed the reactivity of interfacial bromines. Reactions with p-trifluoromethylanilinium chloride probed the exchange reactivity of the Cs+ cation. A complex-forming ligand, 4,4’-bis(trifluoromethyl)-2,2’-bipyridine, probed for interfacial Sn2+- site cations. For Cs2TiBr6, both BF3 and (C6F5)3B probed the reactivity of interfacial bromines. Fluorine features in x-ray photoelectron spectroscopy (XPS) quantified reaction outcomes for each solution-phase species. XPS indicated adsorption of BF3 on CsSnBr3 and (C6F5)3B on Cs2TiBr6 indicating surface-available halide anions on both surfaces. For CsSnBr3, temperature- programmed desorption (TPD) quantified a ~215 kJ mol–1 desorption energy of BF3 on the surface. Adsorption of the fluorinated anilinium cation included no concomitant adsorption of chlorine as revealed by the absence of Cl 2p features within the limits of XPS detection. The bipyridine ligand demonstrated adsorption to CsSnBr3. We discuss the present results in the context of interfacial stability, passivation, and reactivity for solar-energy conversion devices.

We quantified the chemical species present at polycrystalline cesium tin bromide perovskite, CsSnBr3 and cesium titanium bromide antifluorite, Cs2TiBr6. For CsSnBr3, experiments utilized the orthogonal reactivity of the Cs+ cation, the Sn2+ cation, and the Br– halide anion. Ambient- pressure exposure to BF3 solutions probed the reactivity of interfacial bromines. Reactions with p-trifluoromethylanilinium chloride probed the exchange reactivity of the Cs+ cation. A complex-forming ligand, 4,4’-bis(trifluoromethyl)-2,2’-bipyridine, probed for interfacial Sn2+- site cations. For Cs2TiBr6, both BF3 and (C6F5)3B probed the reactivity of interfacial bromines. Fluorine features in x-ray photoelectron spectroscopy (XPS) quantified reaction outcomes for each solution-phase species. XPS indicated adsorption of BF3 on CsSnBr3 and (C6F5)3B on Cs2TiBr6 indicating surface-available halide anions on both surfaces. For CsSnBr3, temperature- programmed desorption (TPD) quantified a ~215 kJ mol–1 desorption energy of BF3 on the surface. Adsorption of the fluorinated anilinium cation included no concomitant adsorption of chlorine as revealed by the absence of Cl 2p features within the limits of XPS detection. The bipyridine ligand demonstrated adsorption to CsSnBr3. We discuss the present results in the context of interfacial stability, passivation, and reactivity for solar-energy conversion devices.

硅對現今科技至關重要。而有機物吸附於硅表面可能大大擴展硅的用途。在本論文中，我採用密度泛函理論研究了六種分子於硅表面的反應。本論文大致可分為四部分。 / 第一部分包含四個分子（吡嗪、吡啶、嘧啶與1,3,5-三氮嗪）的吸附研究。它們都擁有類似於苯的結構而環中又包含氮原子。分子可以用氮原子與表面形成配位鍵並作為進一步反應的前體故其反應更為容易預測。而反應通常只消除π 鍵而不會使分子分解這使得分子可以在平衡狀態下與表面生成最為穩定的結構。此兩種特性使它們成為硅表面吸附的絶佳研究對象。不同的實驗都顯示出吡嗪於硅表面只會生成Cross-row bridge 結構加熱硅表面更會促進納米線的生成。過往的計算無法解釋實驗結果而我的計算表明范德華力對導出正確計算結果非常重要加入范德華力的修正可以同時解釋單一產物與納米線的生成。吡啶的吸附實驗結果相比之下較為複雜。低溫下的吸附與飽和只生成兩種產物可是室溫下的實驗卻顯示多種產物並存於表面。加入范德華力的計算結果指出覆蓋度和溫度與吸附密切相關並指出對低溫下形成的飽和表面加溫可能促使納米線的生成。而於室溫下吡啶可進入多條反應路徑致使多種產物於表面並存。基於范德華力對這兩個分子的顯著影響我又將此效應加諸於嘧啶與1,3,5-三氮嗪的吸附研究。結果表明於低覆蓋度與低溫下它們只生成Double-dative 產物。然而增加覆蓋度會使Double-dative 的能量高於其它產物導致多種產物並存。由於嘧啶與1,3,5-三氮嗪都可生成一種特別的tight-bridge 結構加溫會使它們輕易解離。對此四種分子的研究顯示出氮原子的數量與位置如何影響吸附過程。 / 第二部分包含對1,2-環己二酮的吸附研究。於室溫下此分子會以互變異構體形式存在。之前的實驗指出它會先變回二酮才進行後續反應這種硅表面輔助互變反應的現象是前所未見的卻無後續研究以驗証其說。我的計算結果指出雖然互變反應的能壘被硅表面大幅降低可是仍不足以與其他反應路徑相匹敵。其中三種新產物既與實驗譜相吻合而反應能壘和能量都低故比之前所提產物更為可取。 / 第三部分包含對氰基苯的吸附研究。之前的三個實驗給出完全不同的結論。探明其與覆蓋度和溫度的關係後我提出氰基苯於低溫下飽和只會生成一種產物。而在室溫下的吸附會先生成valley-bridge 結構增加覆蓋度將使多種產物並存。計算結果不但表明有序吸附的可能性同時又解釋為何不同實驗給出看似不相容的結論。 / Silicon is an important material and substrate in modern technologies. Adsorption of organic molecules on silicon surface has attracted much attention due to the possibility of functionalizing the surface. In this thesis, density functional theory has been applied to study the adsorption of several organic molecules on Si(100) surface. / Results on the adsorption of benzene-like N-heteroaromatic molecules on Si(100)surface, including pyrazine, pyridine, pyrimidine and s-triazine, are presented in Chapters 2-4. This class of molecules, containing nitrogen atoms, can datively attach to dimer and act as precursor for further reaction. Thus, their reactions on surface can be easily predicted. Their reaction with surface would sacrifice π bond rather than dissociation under very mild condition such that the most stable adsorption product can be obtained under thermal equilibrium. These two properties of N-heteroaromatic compounds makes them good models for the study of reaction on surface Experiments repeatedly showed that pyrazines formed cross-row bridge structures on Si(100) under various conditions, and thermal annealing led to the formation of ordered nano-lines. Previous calculations did not explain these observations. This thesis demonstrates that addition of van der Waals (vdW) correction is critical to explain the formation of both the cross-row bridge and the nano-lines. For pyridine, the situation is more complex. Only two products were observed in low temperature adsorption experiments. In contrast, room temperature experiments yielded a mixture of products. With vdW corrections added, results show that pyridine adsorption is dependent on both coverage and temperature. Adsorption and saturation started at low temperature and followed by annealing may produce nano-lines consisted of cross-row bridge structures. Adsorption at room temperature opens up all reaction channels such that nano-line formation becomes difficult, which explains the discrepancy among experimental studies. In light of these results, the pyrimidine and s-triazine adsorption on Si(100) are also explored. The results show that they form double-dative structures at low coverage and low temperature. Increasing coverage will destabilize it and lead to mixture of products. These structures decompose easily upon heating due to the formation of a particular tight-bridge structure. These results show that the position and number of heteroatom are important to explain the difference in reaction selectivity among N-heteroaromatic molecules. For all four molecules, cooperative effect and the addition of vdW correction, which are almost neglected in similar study, are shown to be important in surface adsorption process. / In Chapter 5, the adsorption of 1,2-cyclohexanedione (1,2-CHD) on surface is studied. Gas molecule of 1,2-CHD exists in the tautomeric form (2-hydroxylcyclohex-2-ene-1-one) at room temperature. Previous experimental studies claimed that surface assisted tautomerization back to 1,2-CHD took place before further reaction, although there was no follow-up study. Computational results showed that although surface adsorption lowers the barrier for tautomerization, the barrier is still at least 5 times larger than other reaction channels. Three new structures are proposed, which are in better agreement with previous spectroscopic results. / In the final chapter, the adsorption of benzonitrile on Si(100) is studied. Three previous experimental studies presented conflicting results. With the coverage and temperature dependence effects clarified, my results suggest that adsorption at saturation and low temperature leads to a single product. Adsorption at room temperature first leads to a valley-bridge structure, while a mixture of adsorption structures is produced upon increasing coverage, which explained the conflicting experimental results. The last two chapters show the importance of computational modeling for interpretation and summarizing experimental results. / Detailed summary in vernacular field only. / Detailed summary in vernacular field only. / Detailed summary in vernacular field only. / Detailed summary in vernacular field only. / Ng, Kwok Hung. / Thesis (Ph.D.) Chinese University of Hong Kong, 2014. / Includes bibliographical references. / Abstracts also in Chinese. / Ng, Kwok Hung.