This book is devoted to the emerging field of techniques for visualizing atomic-scale properties of active catalysts under actual working conditions, i.e. high gas pressures and high temperatures. It explains how to understand these observations in terms of the surface structures and dynamics and their detailed interplay with the gas phase. This provides an important new link between fundamental surface physics and chemistry, and applied catalysis. The book explains the motivation and the necessity of operando studies, and positions these with respect to the more traditional low-pressure investigations on the one hand and the reality of industrial catalysis on the other. The last decade has witnessed a rapid development of new experimental and theoretical tools for operando studies of heterogeneous catalysis. The book has a strong emphasis on the new techniques and illustrates how the challenges introduced by the harsh, operando conditions are faced for each of these new tools. Therefore, one can also read this book as a collection of recipes for the development of operando instruments. At present, the number of scientific results obtained under operando conditions is still limited and mostly focused on a simple test reaction, the catalytic oxidation of CO. This reaction thus forms a natural binding element between the chapters, linking the demonstrations of new techniques, and also connecting the theoretical and experimental studies. Some first results on other reactions are also presented. If there is one thing that can be concluded already in this early stage, it is that the catalytic conditions themselves can have dramatic effects on the structure and composition of the surfaces of catalysts, which, in turn can greatly affect the mechanisms, the activity, and the selectivity of the chemical reactions that they catalyze.

In this new textbook on physical chemistry, fundamentals are introduced simply yet in more depth than is common. Topics are arranged in a progressive pattern, with simpler theory early and more complicated theory later. General principles are induced from key experimental results. Some mathematical background is supplied where it would be helpful. Each chapter includes worked-out examples and numerous references. Extensive problems, review, and discussion questions are included for each chapter. More detail than is common is devoted to the nature of work and heat and how they differ. Introductory Caratheodory theory and the standard integrating factor for dGrev are carefully developed. The fundamental role played by uncertainty and symmetry in quantum mechanics is emphasized. In chemical kinetics, various methods for determined rate laws are presented. The key mechanisms are detailed. Considerable statistical mechanics and reaction rate theory are then surveyed. Professor Duffey has given us a most readable, easily followed text in physical chemistry.

Electrochemistry plays an important role in preserving our cultural heritage. For the first time this has been documented in the present volume. Coverage includes both electrochemical processes such as corrosion and electroanalytical techniques allowing to analyse micro- and nanosamples from works of art or archaeological finds. While this volume is primarily aimed at electrochemists and analytical chemists, it also contains relevant information for conservators, restorers, and archaeologists.

The series Structure and Bonding publishes critical reviews on topics of research concerned with chemical structure and bonding. The scope of the series spans the entire Periodic Table and addresses structure and bonding issues associated with all of the elements. It also focuses attention on new and developing areas of modern structural and theoretical chemistry such as nanostructures, molecular electronics, designed molecular solids, surfaces, metal clusters and supramolecular structures. Physical and spectroscopic techniques used to determine, examine and model structures fall within the purview of Structure and Bonding to the extent that the focus is on the scientific results obtained and not on specialist information concerning the techniques themselves. Issues associated with the development of bonding models and generalizations that illuminate the reactivity pathways and rates of chemical processes are also relevant. The individual volumes in the series are thematic. The goal of each volume is to give the reader, whether at a university or in industry, a comprehensive overview of an area where new insights are emerging that are of interest to a larger scientific audience. Thus each review within the volume critically surveys one aspect of that topic and places it within the context of the volume as a whole. The most significant developments of the last 5 to 10 years should be presented using selected examples to illustrate the principles discussed. A description of the physical basis of the experimental techniques that have been used to provide the primary data may also be appropriate, if it has not been covered in detail elsewhere. The coverage need not be exhaustive in data, but should rather be conceptual, concentrating on the new principles being developed that will allow the reader, who is not a specialist in the area covered, to understand the data presented. Discussion of possible future research directions in the area is welcomed. Review articles for the individual volumes are invited by the volume editors. Readership: research scientists at universities or in industry, graduate students Special offer For all customers who have a standing order to the print version of Structure and Bonding, we offer free access to the electronic volumes of the Series published in the current year via SpringerLink.

Li-Co-Mn-Ni oxides have been of extreme interest as potential positive electrode materials for next generation Li-ion batteries. Though many promising materials have been discovered and studied extensively, much debate remains in the literature about the structures of these materials. There is no consensus as to whether the lithium-rich layered materials are single-phase or form a layered-layered composite on the few nanometer length-scales. Much of this debate came about because no phase diagrams existed to describe these systems under the synthesis conditions used to make electrode materials. Detailed in this thesis are the complete Li-Co-Mn-O and Li-Mn-Ni-O phase diagrams generated by way of the combinatorial synthesis of mg-scale samples at over five hundred compositions characterized with X-ray diffraction. Selected bulk samples were used to confirm that the findings are relevant to synthesis conditions used commercially. The results help resolve a number of points of confusion and contradiction in the literature. Amongst other important findings, the compositions and synthesis conditions giving rise to layered-layered nano-composites are presented and electrochemical results are used to show how better electrode materials can be achieved by making samples in the single phase-layered regions.

The hydrogen bond represents an important interaction between molecules, and the dynamics of hydrogen bonds in water create an ever-present question associated with the process of chemical and biological reactions. In spite of numerous studies, the process remains poorly understood at the microscopic level because hydrogen-bond dynamics, such as bond rearrangements and hydrogen/proton transfer reactions, are extremely difficult to probe. Those studies have been carried out by means of spectroscopic methods where the signal stems from the ensemble of a system and the hydrogen-bond dynamics were inferred indirectly. This book addresses the direct imaging of hydrogen-bond dynamics within water-based model systems assembled on a metal surface, using a scanning tunneling microscope (STM). The dynamics of individual hydrogen bonds in water clusters, hydroxyl clusters, and water-hydroxyl complexes are investigated in conjunction with density functional theory. In these model systems, quantum dynamics of hydrogen bonds, such as tunneling and zero-point nuclear motion, are observed in real space. Most notably, hydrogen atom relay reactions, which are frequently invoked across many fields of chemistry, are visualized and controlled by STM. This work presents a means of studying hydrogen-bond dynamics at the single-molecule level, providing an important contribution to wide fields beyond surface chemistry.

This thesis addresses two fundamental areas in contemporary organic chemistry: synthesis of natural products and catalytic asymmetric synthesis. Firstly, a new methodology, developed by our research group, which allows the asymmetric synthesis of lactones, a structural unit ubiquitous in natural products, was utilised in the synthesis of a number of natural product analogues that showed significant biological activity. Secondly, the development of a catalytic asymmetric synthesis of a key structural motif present in a number of natural products and pharmaceuticals was accomplished. During the course of this work we discovered dual stereo control, which is significant because it allows the configuration of a new stereo centre to be controlled by a simple change of proton source.

This book covers the results obtained in the Tera op Workbench project during a four years period from 2004 to 2008. The Tera op Workbench project is a colla- ration betweenthe High PerformanceComputingCenter Stuttgart (HLRS) and NEC Deutschland GmbH (NEC-HPCE) to support users to achieve their research goals using high performance computing. The Tera op Workbench supports users of the HLRS systems to enable and - cilitate leading edge scienti c research. This is achieved by optimizing their codes and improving the process work ow which results from the integration of diff- ent modules into a "hybrid vector system". The assessment and demonstration of industrial relevance is another goal of the cooperation. The Tera op Workbench project consists of numerous individual codes, grouped together by application area and developed and maintained by researchers or c- mercial organizations. Within the project, several of the codes have shown the ab- ity to reach beyond the TFlop/s threshold of sustained performance. This created the possibility for new science and a deeper understanding of the underlying physics. The papers in this book demonstrate the value of the project for different scienti c areas.

Chemical Modelling: Applications and Theory comprises critical literature reviews of molecular modelling, both theoretical and applied. Molecular modelling in this context refers to modelling the structure, properties and reactions of atoms, molecules and materials. Each chapter is compiled by experts in their fields and provides a selective review of recent literature. With chemical modelling covering such a wide range of subjects, this Specialist Periodical Report serves as the first port of call to any chemist, biochemist, materials scientist or molecular physicist needing to acquaint themselves of major developments in the area. Specialist Periodical Reports provide systematic and detailed review coverage in major areas of chemical research. Compiled by teams of leading authorities in the relevant subject areas, the series creates a unique service for the active research chemist, with regular, in-depth accounts of progress in particular fields of chemistry. Subject coverage within different volumes of a given title is similar and publication is on an annual or biennial basis. Current subject areas covered are Amino Acids, Peptides and Proteins, Carbohydrate Chemistry, Catalysis, Chemical Modelling. Applications and Theory, Electron Paramagnetic Resonance, Nuclear Magnetic Resonance, Organometallic Chemistry. Organophosphorus Chemistry, Photochemistry and Spectroscopic Properties of Inorganic and Organometallic Compounds. From time to time, the series has altered according to the fluctuating degrees of activity in the various fields, but these volumes remain a superb reference point for researchers.

The second supplement to the three volume reference work Comprehensive Asymmetric Catalysis critically reviews new developments to the hottest topics in the field written by recognised experts. Seven chapters which are already in the major reference work have been supplemented and additionally a new chapter on Aminohydroxylation of Carbon-Carbon Double Bonds has been included. Thus, the state of the art in this area is now re-established. Together with the basic three volume book set and Supplement 1 it is not only the principal reference source for synthetic organic chemists, but also for all scientific researchers who use chiral compounds in their work (for example, in biochemical investigations and molecular medicine) as well as for pharmaceutical chemists and other industrial researchers who prepare chiral compounds.

As the title suggests, Isotope Effects in the Chemical, Geological and Bio Sciences deals with differences in the properties of isotopically substituted molecules, such as differences in the chemical and physical properties of water and the heavy waters. Since the various fields in which isotope effects are applied do not only share fundamental principles but also experimental techniques, this book includes a discussion of experimental apparatus and experimental techniques.

Isotope Effects in the Chemical, Geological and Bio Sciences is an educational monograph addressed to graduate students and others undertaking isotope effect research. The fundamental principles needed to understand isotope effects are presented in appropriate detail. While it is true that these principles are more familiar to students of physical chemistry and some background in physical chemistry is recommended, the text provides enough detail to make the book an asset to students in organic and biochemistry, and geochemistry.

Magnetic resonance techniques are especially interesting in the study of colloids and interfaces due to their unique ability to elucidate structure, dynamics and function at the atomic and molecular level. This book illustrates the most up to date applications of innovative NMR and EPR techniques, including magnetic resonance imaging and microscopy, to gas-solid and liquid-solid interfaces, organic and biological surfaces, microemulsions, liquid crystals, membranes, structure and dynamics of polymers and micellar systems, and diffusion in heterogeneous systems.

A compendium of advanced NMR and EPR techniques and a state of the art description of the power of advanced new methodologies for the study of molecular dynamics and interfaces.

What happens when a chemical is released into the environment? It diffuses, disperses, adsorbs, reacts, and/or changes state. To predict and analyze this process, the mathematics of diffusion is applied to lakes, rivers, groundwater, the atmosphere, the oceans, and transport between these media. A sustainable world requires a deep understanding of the transport of chemicals through the environment and how to address and harness this process. This volume presents a succinct and in-depth introduction to this critical topic. Featuring authoritative, peer-reviewed articles from the Encyclopedia of Sustainability Science and Technology, Transport and Fate of Chemicals in the Environment represents an essential one-stop reference for an audience of researchers, undergraduate and graduate students, and industry professionals.

The breadth of scientific and technological interests in the general topic of photochemistry is truly enormous and includes, for example, such diverse areas as microelectronics, atmospheric chemistry, organic synthesis, non-conventional photoimaging, photosynthesis, solar energy conversion, polymer technologies, and spectroscopy. This Specialist Periodical Report on Photochemistry aims to provide an annual review of photo-induced processes that have relevance to the above wide-ranging academic and commercial disciplines, and interests in chemistry, physics, biology and technology. In order to provide easy access to this vast and varied literature, each volume of Photochemistry comprises sections concerned with photophysical processes in condensed phases, organic aspects which are sub-divided by chromophore type, polymer photochemistry, and photochemical aspects of solar energy conversion. Volume 34 covers literature published from July 2001 to June 2002. Specialist Periodical Reports provide systematic and detailed review coverage in major areas of chemical research. Compiled by teams of leading authorities in the relevant subject areas, the series creates a unique service for the active research chemist, with regular, in-depth accounts of progress in particular fields of chemistry. Subject coverage within different volumes of a given title is similar and publication is on an annual or biennial basis.

The series Topics in Current Chemistry presents critical reviews of the present and future trends in modern chemical research. The scope of coverage is all areas of chemical science including the interfaces with related disciplines such as biology, medicine and materials science. The goal of each thematic volume is to give the non-specialist reader, whether in academia or industry, a comprehensive insight into an area where new research is emerging which is of interest to a larger scientific audience. Each review within the volume critically surveys one aspect of that topic and places it within the context of the volume as a whole. The most significant developments of the last 5 to 10 years are presented using selected examples to illustrate the principles discussed. The coverage is not intended to be an exhaustive summary of the field or include large quantities of data, but should rather be conceptual, concentrating on the methodological thinking that will allow the non-specialist reader to understand the information presented. Contributions also offer an outlook on potential future developments in the field. Review articles for the individual volumes are invited by the volume editors. Readership: research chemists at universities or in industry, graduate students.

There is an increasing challenge for chemical industry and research institutions to find cost-efficient and environmentally sound methods of converting natural resources into fuels chemicals and energy. Catalysts are essential to these processes and the Catalysis Specialist Periodical Report series serves to highlight major developments in this area. This series provides systematic and detailed reviews of topics of interest to scientists and engineers in the catalysis field. The coverage includes all major areas of heterogeneous and homogeneous catalysis and also specific applications of catalysis such as NOx control kinetics and experimental techniques such as microcalorimetry. Each chapter is compiled by recognised experts within their specialist fields and provides a summary of the current literature. This series will be of interest to all those in academia and industry who need an up-to-date critical analysis and summary of catalysis research and applications. Catalysis will be of interest to anyone working in academia and industry that needs an up-to-date critical analysis and summary of catalysis research and applications. Specialist Periodical Reports provide systematic and detailed review coverage in major areas of chemical research. Compiled by teams of leading experts in their specialist fields, this series is designed to help the chemistry community keep current with the latest developments in their field. Each volume in the series is published either annually or biennially and is a superb reference point for researchers. www.rsc.org/spr

The study of physical adsorption has enormous economic and technical value, while continuing to present significant scientific challenges. During the last few years three significant trends have become manifest: significant theoretical advances; instrumental developments allowing detailed characterization of materials, including microporous solids; and the realization that closer coupling of scientific and technological lines of enquiry can lead to both greater scientific understanding and better technology. Topics covered include: the dramatic progress in theoretical analysis; breakthroughs in experimentation; the unique aspects of transport in micropores; and the application of physical adsorption in industrial processes. Audience: Specialized workers will find the updated material invaluable. University lecturers may use material in the book for introductory or graduate courses. The extensive literature references point to further detailed studies.

Seven review articles and original papers provide a representative overview of the research work done in hydrogen bond research at Austrian universities. The topics covered by the contributions are: state-of-the-art of understanding hydrogen bonding in biopolymers; recent NMR techniques for studying hydrogen bonding in aqueous solutions; intramolecular hydrogen bonding and proton transfer in a class of Mannich bases derived from substituted phenols and naphthols; competition between intramolecular hydrogen bonds in ortho-disubstituted phenols; molecular dynamic simulations on proton transfer in 5,8-dihydroxynaphthoquinone and in the formic acid dimer; accurate calculations of the intermolecular interactions in cyanoacetylen dimers; correlation between OH...O bond distances and OH stretching frequencies as derived from structural and spectroscopic data of minerals.

Advances in Quantum Chemistry presents surveys of current developments in this rapidly developing field that falls between the historically established areas of mathematics, physics, chemistry, and biology. With invited reviews written by leading international researchers, each presenting new results, it provides a single vehicle for following progress in this interdisciplinary area.

This thesis demonstrates the novel magnetic functionalities in cyanido-bridged metal assemblies, and as such appeals to readers in the field of materials science. The utilization of octacyanidometalates as building blocks enables the observation of (i) photo-induced magnetization due to a light-induced spin-crossover in an iron octacyanidoniobate-based assembly, (ii) photo-induced magnetization with a two-step spin-crossover behavior in an iron octacyanidoniobate-based material, and (iii) the coexistence of super-ionic conductivity and metamagnetism in a manganese-octacyanoniobate system. These multi-functionalities are achieved by incorporating a spin-crossover moiety or a hydrogen-bonding network into a cyanido-bridged network structure with a strong magnetic interaction. In particular, in light-induced spin-crossover magnets, a magnetically non-ordered state can be altered to a magnetically ordered state by photo-irradiation, which is one of the attractive mechanisms for novel optical switching devices.

This book explores the conversion for solar energy into renewable liquid fuels through electrochemical reactions. The first section of the book is devoted to the theoretical fundamentals of solar fuels production, focusing on the surface properties of semiconductor materials in contact with aqueous solutions and the reaction mechanisms. The second section describes a collection of current, relevant characterization techniques, which provide essential information of the band structure of the semiconductors and carrier dynamics at the interface semiconductor. The third, and last section comprises the most recent developments in materials and engineered structures to optimize the performance of solar-to-fuel conversion devices.

This book covers the results of investigations into the mechanisms and kinetics of thermal decompositions of solid and liquid substances on the basis of thermochemical analyses of the processes. In the framework of the proposed ideas, the main features of these reactions are explained and many problems and unusual phenomena, which have accumulated in this field, are interpreted. New methods of TA measurement and calculation have been developed, which permit the precision and accuracy of determination of kinetic parameters to be increased substantially. Reliable kinetic characteristics have been obtained and the decomposition mechanisms for several tens of substances have been interpreted. These include different classes of compounds: crystalline hydrates, oxides, hydroxides, nitrides, azides, nitrates, sulfates, carbonates and oxalates.

The PUILS series delivers up-to-date reviews of progress in Ultrafast Intense Laser Science, a newly emerging interdisciplinary research field spanning atomic and molecular physics, molecular science, and optical science, which has been stimulated by the recent developments in ultrafast laser technologies. Each volume compiles peer-reviewed articles authored by researchers at the forefront of each their own subfields of UILS. Every chapter opens with an overview of the topics to be discussed, so that researchers unfamiliar to the subfield, as well as graduate students, can grasp the importance and attractions of the research topic at hand; these are followed by reports of cutting-edge discoveries. This ninth volume covers a broad range of topics from this interdisciplinary research field, focusing on ultrafast molecular responses to an intense laser field, advanced techniques for attosecond pulse generation, atomic and molecular responses to attosecond pulses, photoelectron spectroscopy of atoms and molecules interacting with intense light fields, and attosecond pulse interaction with solid materials.

At present, three-dimensional free-radical polymerization (TFRP) is a special ?eld of radical polymerization. TFRP is characterized by speci?c kinetic regularities and mechanisms of processes for the formation of cross-linked or hyper-branched po- mers, and they are different from the kinetics and mechanism of classical radical polymerization. The fundamental studies of kinetics and mechanism of TFRP with formation of cross-linked polymers have been carried out in three stages. The ?rst stage lasted from 1960 until 1983, and the main mechanisms of TFRP of oligo(acrylates) were established during this stage [1-3]. Condensation telomerization, being a universal oligo(acrylate) synthesis procedure, allows us to vary certain molecular parameters, such as length and ?exibility of oligomeric blocks, number and type of reactive groups (methacrylic or acrylic groups), and chemical nature of atomic groups of an oligomeric block, which represent the centers of strong intermolecular interactions. For this reason, oligo(acrylates) were very convenient compounds for establi- ing the main kinetic regularities of TFRP and regularities of formation of polymer three-dimensional cross-linkedstructures,according totheso-calledmicrohetero- neous mechanism (G.V. Korolev, 1977), at the topological and morphological levels.