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Books > Science & Mathematics > Chemistry > Physical chemistry
This book presents a range of fundamentally new approaches to solving problems involving traditional molecular models. Fundamental molecular symmetry is shown to open new avenues for describing molecular dynamics beyond standard perturbation techniques. Traditional concepts used to describe molecular dynamics are based on a few fundamental assumptions, the ball-and-stick picture of molecular structure and the respective perturbative treatment of different kinds of couplings between otherwise separate motions. The book points out the conceptual limits of these models and, by focusing on the most essential idea of theoretical physics, namely symmetry, shows how to overcome those limits by introducing fundamentally new concepts. The book begins with an introduction to molecular symmetry in general, followed by a discussion of nuclear spin symmetry. Here, a new correlation between identical particle exchange and spin angular momentum symmetry of nuclei is exhibited. The central part of the book is the discussion of extremely floppy molecules, which are not describable in the framework of traditional theories. The book introduces a fundamentally new approach to describing the molecular dynamics of these molecules - the super-rotor model, which is based on a five-dimensional symmetry that has never been observed in molecules before. By applying the super-rotor theory to the prototype of floppy molecules, protonated methane, this model can consistently predict the symmetry and energy of low-energy states, which were characterized experimentally only a few years ago. The theoretical predictions agree with the experimental results, which makes the prospect of further developing the super-rotor theory and applying it to other molecules a promising one. In the final section, the book also covers the topic of ultrafast rotations, where usual quantum calculations reach their natural limits. A semi-classical method for determining rotational energies, developed in the early 1990s, is shown to be attachable to quantum calculations of the vibrational states. This new combined method is suitable for efficiently calculating ro-vibrational energies, even for molecular states with large angular momentum.
This book presents a comprehensive overview of nanoscale electronics and systems packaging, and covers nanoscale structures, nanoelectronics packaging, nanowire applications in packaging, and offers a roadmap for future trends. Composite materials are studied for high-k dielectrics, resistors and inductors, electrically conductive adhesives, conductive "inks," underfill fillers, and solder enhancement. The book is intended for industrial and academic researchers, industrial electronics packaging engineers who need to keep abreast of progress in their field, and others with interests in nanotechnology. It surveys the application of nanotechnologies to electronics packaging, as represented by current research across the field.
This book presents current research into the catalytic combustion of methane using perovskite-type oxides (ABO3). Catalytic combustion has been developed as a method of promoting efficient combustion with minimum pollutant formation as compared to conventional catalytic combustion. Recent theoretical and experimental studies have recommended that noble metals supported on (ABO3) with well-ordered porous networks show promising redox properties. Three-dimensionally ordered macroporous (3DOM) materials with interpenetrated and regular mesoporous systems have recently triggered enormous research activity due to their high surface areas, large pore volumes, uniform pore sizes, low cost, environmental benignity, and good chemical stability. These are all highly relevant in terms of the utilization of natural gas in light of recent catalytic innovations and technological advances. The book is of interest to all researchers active in utilization of natural gas with novel catalysts. The research covered comes from the most important industries and research centers in the field. The book serves not only as a text for researcher into catalytic combustion of methane, 3DOM perovskite mixed oxide, but also explores the field of green technologies by experts in academia and industry. This book will appeal to those interested in research on the environmental impact of combustion, materials and catalysis.
The book is a short primer on chemical reaction rates based on a six-lecture first-year undergraduate course taught by the author at the University of Oxford. The book explores the various factors that determine how fast or slowly a chemical reaction proceeds and describes a variety of experimental methods for measuring reaction rates. The link between the reaction rate and the sequence of steps that makes up the reaction mechanism is also investigated. Chemical reaction rates is a core topic in all undergraduate chemistry courses.
This thesis addresses the coordination chemistry and reactivity of copper and gold complexes with a focus on the elucidation of (i) the metal-mediated activation of -bonds and (ii) the migratory insertion reaction. Both processes are of considerable importance in organometallic chemistry, but remain elusive for Cu and Au complexes. In this work, the author contributes significant advances: The first -SiH complexes of copper are experimentally and computationally characterized, yielding valuable insights into -bond activation processes for copper. Evidence for a highly unusual migratory syn insertion of unsaturated organic molecules into the gold-silicon bond of silylgold (I) complexes is provided and the corresponding mechanism identified. The intermolecular oxidative addition of -SiSi, -CC and -CX (X=halogen) bonds with molecular gold (I) complexes is studied in detail, effectively demonstrating that this reaction, usually considered to be impossible for gold, is actually highly favored, provided an adequate ligand is employed. The use of small-bite angle bis (phosphine) gold (I) complexes allows for the first time the oxidative addition of -CC and -CX bonds for gold (I). These results shed light on an unexpected reactivity pattern of gold complexes and may point the way to 2-electron redox transformations mediated by this metal, opening up new perspectives in gold catalysis.
This book explores new experimental phase diagrams of non-oxide ceramics, with a particular focus on the silicon nitride, silicon carbide and aluminum nitride, as well as the ultra-high temperature ceramic (UHTC) systems. It features more than 80 experimental phase diagrams of these non-oxide ceramics, including three phase diagrams of UHTC systems, constructed by the authors. Physical chemistry data covering the period since the 1970s, collected by the author Z.K.Huang, is presented in six tables in the appendixes. It also includes 301 figures involving about 150 material systems. Most of the phase diagrams have been selected from the ACerS-NIST database with copyright permission. The book methodically presents numerous diagrams previously scattered in various journals and conferences worldwide. Providing extensive experimental data, it is a valuable reference resource on ceramics development and design for academic researchers, R&D engineers and graduate students.
This book discusses the development of various reliable scanning electrochemical microscopy (SECM) imaging techniques for studying the distribution of biomarkers and nanomaterials in thin and thick animal samples, plant antioxidant (AO) defense systems, as well as human melanoma. The authors demonstrate that SECM could improve the diagnosis and understanding of different melanoma stages on the basis of highly resolved maps of the tyrosinase distribution. Tyrosinase is the key enzyme involved in fruit maturation and is a biomarker for melanoma. As such the book presents various tyrosinase SECM detection strategies developed for the analysis of the spatial distribution of tyrosinase in melanoma and in banana samples. It describes the first imaging of the redox active proteins within the entire mouse heart with an SECM system using a spider probe composed of eight independent microelectrodes. Further, it investigates distributions of injected graphene nanoribbons (GONRs) for drug delivery by Soft-Probe-SECM. Lastly, the book outlines a non-invasive electrochemical strategy for mapping the AO activity of apple peel using Soft-Probe-SECM.
This book is exceptional in offering a thorough but accessible introduction to calorimetry that will meet the needs of both students and researchers in the field of particle physics. It is designed to provide the sound knowledge of the basics of calorimetry and of calorimetric techniques and instrumentation that is mandatory for any physicist involved in the design and construction of large experiments or in data analysis. An important feature is the correction of a number of persistent common misconceptions. Among the topics covered are the physics and development of electromagnetic showers, electromagnetic calorimetry, the physics and development of hadron showers, hadron calorimetry, and calibration of a calorimeter. Two chapters are devoted to more promising calorimetric techniques for the next collider. Calorimetry for Collider Physics, an introduction will be of value for all who are seeking a reliable guide to calorimetry that occupies the middle ground between the brief chapter in a generic book on particle detection and the highly complex and lengthy reference book.
The present work focuses on the development of intensified small-scale extraction units for spent nuclear fuel reprocessing using advanced process engineering with combined experimental and modelling methodologies. It discusses a number of novel elements, such as the intensification of spent fuel reprocessing and the use of ionic liquids as green alternatives to organic solvents. The use of ionic liquids in two-phase liquid-liquid separation is new to the Multiphase Flow community, and has proved to be challenging, especially in small channels, because of the surface and interfacial properties involved, which are very different to those of common organic solvents. Numerical studies have been also performed to couple the hydrodynamics at small scale with the mass transfer. The numerical results, taken together with scale-up studies, are used to evaluate the applicability of the small-scale units in reprocessing large volumes of nuclear waste.
Describing non-equilibrium "cold" plasmas through a chemical physics approach, this book uses the state-to-state plasma kinetics, which considers each internal state as a new species with its own cross sections. Extended atomic and molecular master equations are coupled with Boltzmann and Monte Carlo methods to solve the electron energy distribution function. Selected examples in different applied fields, such as microelectronics, fusion, and aerospace, are presented and discussed including the self-consistent kinetics in RF parallel plate reactors, the optimization of negative ion sources and the expansion of high enthalpy flows through nozzles of different geometries. The book will cover the main aspects of the state-to-state kinetic approach for the description of nonequilibrium cold plasmas, illustrating the more recent achievements in the development of kinetic models including the self-consistent coupling of master equations and Boltzmann equation for electron dynamics. To give a complete portrayal, the book will assess fundamental concepts and theoretical formulations, based on a unified methodological approach, and explore the insight in related scientific problems still opened for the research community.
Macroscopic cellular structures and functions are generally investigated using biological and biochemical approaches. But these methods are no longer adequate when one needs to penetrate deep into the small-scale structures and understand their functions. The cell is found to hold various physical structures, molecular machines, and processes that require physical and mathematical approaches to understand and indeed manipulate them. Disorders in general cellular compartments, perturbations in single molecular structures, drug distribution therein, and target specific drug-binding, etc. are mostly physical phenomena. This book will show how biophysics has revolutionized our way of addressing the science and technology of nanoscale structures of cells, and also describes the potential for manipulating the events that occur in them.
Synergetics is the quantitative study of multicomponent systems
that exhibit nonlinear dynamics and cooperativity. This book
specifically considers basic models of the nonlinear dynamics of
molecular systems and discusses relevant applications in biological
physics and the polymer sciences.
This thesis describes novel strategies for the rational design of several cutting-edge high-efficiency photocatalysts, for applications such as water photooxidation, reduction, and overall splitting using a Z-Scheme system. As such, it focuses on efficient strategies for reducing energy loss by controlling charge transfer and separation, including novel faceted forms of silver phosphate for water photooxidation at record high rates, surface-basic highly polymerised graphitic carbon nitride for extremely efficient hydrogen production, and the first example of overall water splitting using a graphitic carbon nitride-based Z-Scheme system. Photocatalytic water splitting using solar irradiation can potentially offer a zero-carbon renewable energy source, yielding hydrogen and oxygen as clean products. These two 'solar' products can be used directly in fuel cells or combustion to provide clean electricity or other energy. Alternatively they can be utilised as separate entities for feedstock-based reactions, and are considered to be the two cornerstones of hydrogenation and oxidation reactions, including the production of methanol as a safe/portable fuel, or conventional catalytic reactions such as Fischer-Tropsch synthesis and ethylene oxide production. The main driving force behind the investigation is the fact that no photocatalyst system has yet reported combined high efficiency, high stability, and cost effectiveness; though cheap and stable, most suffer from low efficiency.
I. Electron Transfer Reactions.- 1. Electron Transfer: General and Theoretical.- 1.1. Overview and General Aspects of Reactions in Fluid Media.- 1.2. Electronic Coupling (Ke1).- 1.2.1. The Distance Dependence of Electron Transfer Rates.- 1.2.2. Electric and Magnetic Field Effects on Electronic Coupling and Related Problems of Photoinduced Electron Transfer.- 1.3. The Free-Energy Dependence of Electron Transfer Reactions: The "Inverted Region" Problem.- 1.4. The Effects of Solvent Dynamics.- 1.5. Metal-to-Metal and Ligand-to-Ligand Charge Transfer ("Inter-valence" Transfer).- 2. Redox Reactions between Two Metal Complexes.- 2.1. Introduction.- 2.2. Reactions of Metal Aqua and Oxo Ions.- 2.2.1. Titanium.- 2.2.2. Vanadium and Chromium.- 2.2.3. Iron.- 2.2.4. Molybdenum and Tungsten.- 2.3. Reactions of Metal Ion Complexes.- 2.3.1. Chromium.- 2.3.2. Manganese.- 2.3.3. Iron, Ruthenium, and Osmium.- 2.3.4. Cobalt and Rhodium.- 2.3.5. Nickel, Palladium, and Platinum.- 2.3.6. Copper and Silver.- 2.3.7. Technetium and Rhenium.- 2.3.8. Ytterbium.- 2.4. Reactions with Metalloproteins.- 2.4.1. Introduction.- 2.4.2. Copper Proteins.- 2.4.3. Hemoglobin and Myoglobin.- 2.4.4. Cytochromes.- 2.4.5. Iron-Sulfur Proteins.- 3. Metal-Ligand Redox Reactions.- 3.1. Introduction.- 3.2. Oxygen, Peroxide, and Other Oxygen Compounds.- 3.2.1. Dioxygen.- 3.2.2. Hydrogen Peroxide.- 3.2.3. Alkyl Hydroperoxides.- 3.3. Nitrogen Compounds and Oxyanions.- 3.3.1. Hydrazine, Azides, Hydroxylamines, and Derivatives.- 3.3.2. Oxynitrogen Compounds.- 3.3.3. Amines and Nitriles.- 3.4. Sulfur Compounds and Oxyanions.- 3.4.1. Peroxodisulfate and Peroxomonosulfate.- 3.4.2. Sulfur Dioxide and Sulfite Ions.- 3.4.3. Sulfoxides.- 3.4.4. Alkyl Sulfur Compounds.- 3.4.5. Selenium, Tellurium, and Elemental Sulfur.- 3.5. Halogen, Halides, and Halogen Oxyanions.- 3.5.1. Halogens.- 3.5.2. Halides.- 3.5.3. Oxyhalogen Compounds.- 3.6. Phosphorus, Arsenic, and Oxycompounds.- 3.6.1. Phosphorus Oxyanions.- 3.6.2. Phosphines and Arsines.- 3.7. Inorganic Radicals.- 3.8. Ascorbic Acid, Quinols, Catechols, and Diols.- 3.8.1. Ascorbic Acid.- 3.8.2. Aromatic Diols and Diones.- 3.8.3. Aromatic and Aliphatic Alcohols.- 3.9. Carboxylic Acids, Carboxylates, Carbon Dioxide, and Carbon Monoxide.- 3.9.1. Carboxylic Acids and Carboxylates.- 3.9.2. Carbon Dioxide and Carbon Monoxide.- 3.10. Alkyl Halides.- 3.11. Organic Radicals.- II. Substitution and Related Reactions.- 4. Reactions of Compounds of the Nonmetallic Elements.- 4.1. Boron.- 4.2. Carbon.- 4.3. Silicon.- 4.4. Germanium.- 4.5. Nitrogen.- 4.6. Phosphorus.- 4.7. Arsenic.- 4.8. Oxygen.- 4.9. Sulfur.- 4.10. Selenium and Tellurium.- 4.11. Halogens, Krypton, and Xenon.- 4.11.1. Fluorine.- 4.11.2. Chlorine.- 4.11.3. Bromine.- 4.11.4. Iodine.- 4.11.5. Krypton and Xenon.- 4.12. Oscillating Reactions.- 5. Substitution Reactions of Inert-Metal Complexes-Coordination Numbers 4 and 5.- 5.1. Introduction.- 5.2. Associative Ligand Exchange at Square-Planar Platinum(II).- 5.3. Associative Ligand Exchange at Square-Planar Palladium(II).- 5.4. Ligand Exchange at Platinum(II) by Dissociative Processes.- 5.5. Ligand Exchange at Nickel.- 5.6. Reactions of Planar Ir(I), Rh(I), Au(III), and Cu(II) Complexes.- 5.7. Five-Coordinate Species.- 5.8.TransEffect.- 5.9. Isomerizations.- 6. Substitution Reactions of Inert-Metal Complexes-Coordination Numbers 6 and Above: Chromium.- 6.1. Introduction.- 6.2. Aquation and Solvolysis of Chromium(III) Complexes.- 6.2.1. [Cr(III)(L5)X]n+1Systems (L = OH2, NH3).- 6.2.2. Cr(III)-C Bond Rupture.- 6.2.3. Amine and Other Complexes.- 6.2.4. Dechelation/Chelation Processes.- 6.2.5. Metal-Ion-Assisted Aquation.- 6.2.6. Porphyrins.- 6.3. Formation of Chromium(III) Complexes.- 6.3.1. The Nature of the Cr3+Cation in Aqueous Solution.- 6.3.2. Anation Reactions.- 6.4. Base Hydrolysis.- 6.5. Oxidation and Reduction of Cr(III) Complexes.- 6.6. Isomerization and Racemization.- 6.7. Photochemistry and Photophysics of Chromium(III) Complexes.-...
In his thesis, Florian Schweinberger investigates the influence of the precise size of catalytically active species on reactivity. In order to do this he carries out studies both in UHV and under ambient conditions for supported, size-selected Platium clusters (8-68 atoms). Schweinberger probed the electronic structure, adsorption properties and reactivity of two olefins on surfaces and Pt clusters in the submonolayer range. With adsorbed trichloroethene (TCE) a possible cluster-adsorbate induced change in the electronic structure, and for ethene a low-temperature, size-dependent self-/hydrogenation was observed.In a collaborative approach, Schweinberger and colleagues investigated Pt clusters under ambient pressure conditions. They characterised the clusters at at the local and integral level and tested for temperature stability. Experiments in gas phase ?-reactors and in liquid, as part of a hybrid photocatalytic system, revealed size-dependent reactivity.Overall this thesis is not only of interest for those who want to perform similar experiments but also provides superb scientific insights for researchers in the field.
The Elementary Reaction Steps in Heterogeneous Catalysis was studies during the first week in November, 1992, by no fewer than 54 participants, drawn from 11 countries, with both industrial and academic backgrounds. The five sessions reported in the book cover: Catalytic reactivity; Surface science studies in catalysis; In situ methods in catalysis; The contribution of theory to catalytic understanding; and Chemical kinetics and chemical engineering. The book ends with Summary lectures, a list of contributors, and an index.
Among the numerous applications of the rare-earth elements, the field of catalysis accounts for a large number. Catalysis represents approximately 20% of the total market sales of rare earths worldwide. As a matter of fact two main applications have been prominent in the last decades: zeolite stabilization for fluid cracking catalysts, and automotive post-combustion catalytic treatment.
This book explores fascinating topics at the edge of life, guiding the reader all the way from the relation of life processes to the second law of thermodynamics and the abundance of complex organic compounds in the universe through to the latest advances in synthetic biology and metabolic engineering. The background to the book is the extraordinary scientific adventures that are being undertaken as progress is made toward the creation of an artificial cell and the control of life processes. This journey involves input from research areas as diverse as genetic engineering, physical chemistry, and information theory. Life is to be thought of not only as a chemical event but also as an information process, with the genome a repository of information gathered over time through evolution. Knowledge of the mechanisms affecting the increase in complexity associated with evolutionary paths is improving, and there appear to be analogies with the evolution of the technologies promoting the development of our society. The book will be of wide interest to students at all levels and to others with an interest in the subject.
This book focuses on the use of bio-inspired and biomimetic methods for the fabrication and activation of nanomaterials. This includes studies concerning the binding of the biomolecules to the surface of inorganic structures, structure/function relationships of the final materials and extensive discussions on the final applications of such biomimetic materials in unique applications including energy harvesting/storage, biomedical diagnostics and materials assembly.
This volume presents the latest developments in the use of organometallic catalysis for the formation of bulk chemicals and the production of energy, via green processes including efficient utilization of waste feedstocks from industry. The chemistry of carbon dioxide relating to its hydrogenation into methanol -an eco-friendly energy storage strategy- and its uses as C1 synthon for the formation of important building-blocks for fine chemicals industry are covered. Catalytic hydrogenations of various functional groups and hydrogen transfer reactions including the use of first row metal catalysts are presented as well as the conversion of alcohols to carboxylates via hydrogen transfer with a zero-waste strategy using water. Transformation of renewable or bio-based raw materials is surveyed through alkene metathesis and C-O bond activations and functionalizations. A green aspect for selective formation of C-C, C-O and C-N bonds involves direct regioselective C-H bond activations and functionalizations. These transformations can now be promoted under mild reaction conditions due to the use photoredox catalyts. C-H bond oxidation using visible light leads mainly to the formation of C-O and C-N bonds, whereas cross-coupled C-C bonds can be formed through the radical additions on (hetero) arenes using photoredox assisted mechanism.
"Computer Simulation in Chemical Physics" contains the proceedings of a NATO Advanced Study Institute held at CORISA, Alghero, Sardinia, in September 1992. In the years that have elapsed since the field was last summarised there have been a number of advances which have significantly expanded the scope of the methods. Good examples are the Car-Parrinello method, which allows the study of materials with itinerant electrons; the Gibbs technique for the direct simulation of liquid vapour phase equilibria; the transfer of scaling concepts from simulations of spin models to more complex systems; and the development of the configurational-biased Monte-Carlo methods for studying dense polymers. The field has also been stimulated by an enormous increase in available computing power and the provision of recent software. All these developments, and more, are discussed in an accessible way here, making the text suitable reading for graduate students and research scientists in both academic and industrial settings.
This volume describes the most recent findings on the structure of ILs interpreted through cutting-edge experimental and theoretical methods. Research in the field of ionic liquids (ILs) keeps a fast and steady pace. Since these new-generation molten salts first appeared in the chemistry and physics landscape, a large number of new compounds has been synthesized. Most of them display unexpected behaviour and possess stunning properties. The coverage in this book ranges from the mesoscopic structure of ILs to their interaction with proteins. The reader will learn how diffraction techniques (small and large angle X-Ray and neutron scattering, powder methods), X-Ray absorption spectroscopies (EXAFS/XANES), optical methods (IR, RAMAN), NMR and calorimetric methods can help the study of ILs, both as neat liquids and in mixtures with other compounds. It will enable the reader to choose the best method to suit their experimental needs. A detailed survey of theoretical methods, both quantum-chemical and classical, and of their predictive power will accompany the exposition of experimental ones. This book is a must read for postgraduate students, for post-docs, and for researchers who are interested in understanding the structural properties of ILs.
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