During the oil embargo, in the winter 1973174, parts of Western Europe present ed an almost war-like aspect on Saturdays and Sundays: no traffic on the high ways, no crowds at ski resorts and other weekend entertainment places, no gaso line at the pumps. Living and teaching then in that part of the world, and discussing the situa tion with our students, we came to the conclusion that it would be timely to col lect the fine chemistry already known at the time in the field of conversion of coal to gasoline and other chemicals, and by this way help to draw the attention to this important alternative to crude oil. The idea of this book was born. The energy shock of the early seventies has been healthy and of great conse quences in chemistry. Large amounts of research money have been put to work since, and our knowledge of the possibilities and limitations of coal-based chemistry has increased enormously. During several years it appeared inap propriate to write a monograph about a topic which was in the midst of such an impetuous development. Nevertheless, we collected, and critically selected, the upcoming work as it appeared in the literature, and also tried to provide some modest input ourselves. Now, ten years later, the situation seems to be settled to a certain degree."

EJB Reviews 1989 offer the collection of all reviews published in the European Journal of Biochemistry in one handy volume. This series of review articles by leading scientists covers emerging and rapidly growing fields of research in fundamental as well as in applied areas of biochemistry, such as medicine, biotechnology, agriculture and nutrition. Novel methodological and technological approaches which stimulate biochemical research are also included. All authors review their field in a very critical, selective, evaluative manner, with emphasis on interdisciplinary aspects wherever possible.

Clusters of Atoms and Molecules I is devoted to theoretical concepts and experimental techniques important in the rapidly expanding field of cluster science. Cluster properties are dicussed for clusters composed of alkali metals, semiconductors, transition metals, carbon, oxides and halides of alkali metals, rare gases, and neutral molecules. The book contains several well-integrated treatments, all prepared by experts. Each contribution starts out as simple as possible and ends with the latest results, so that the book can serve as a text for a course, an introduction into the field, or as a reference book for the expert.

Considering aspects of symmetry rules in chemistry, one is faced with con tradictory terms as for example, "90 % concertedness" sometimes being used in literature. To accept conservation of orbital symmetry to be as controlled as inversion by alternative principles seems far more promising. The intention of this book is aimed at introducing a qualitative understanding of phase rela tions in electromagnetic interactions. Avoiding one-sided dogmatism we tried to demonstrate the importance of alternative principles as guidelines to the evolution of alternative order in chemical systems. Passing through the jungle of information it became extremly important to control again and again our insights into the ordering phenomena by experi ments under conditions as coherent as possible. We became more aware of the fact that chemistry - the science of "becoming" in complex systems - can not be understood by mechanistic details, i. e. THROUGHPUT-studies alone, because the mechanism is only true for the special system under inves tigation and does not offer a tool for the evolution of opposite order. We had to accept chemistry as a mediator between molecular physics and general epistemology. This quite unusual combination was directed by excel lent teachers and the realizations were made possible by enthusiastic, open minded coworkers (see references). The next target we will strive for on this journey will be to quantify the alternative principles, that means obtaining the order parameters of H. Haken (e. g. in asymmetric synthesis).

The intensification of the production of silicate materials and products makes a de tailed theoretical study of the processes underlying their manufacture and service more and more urgent. The thermodynamic method is of great importance for studying chemical reac tions of silicate technology. Together with a study of the rate and mechanism of sub stance transfer, it permits obtaining necessary data for the efficient operation of technological processes. The progress of science in recent years has solved numerous problems in the field of the physical chemistry of silicates. The great progress in deciphering silicate structures, and working out methods of the synthesis of minerals and studying their properties must be mentioned. New methods of determining thermic constants have appeared. In future these methods should be more widely used for determining the heats of the silicate forma tion and related compounds in crystalline and vitreous state. This concerns in par ticular the system - CaO - Ab03 - Fe203 - Si0 - H 0 -which is of great impor 2 2 tance for the technology of cement and concrete, ceramics, refractories and glass."

The recent discovery of high-temperature superconductivity in copper based oxides is an event of major importance not only with respect to the physical phenomenon itself but also because it definitely shows that solid state chemistry, and especially the crystal chemistry of oxides, has a crucial place in the synthesis and understanding of new materials for future appli cations. The numerous papers published in the field of high Tc supercon ductors in the last five years demonstrate that the great complexity of these materials necessitates a close collaboration between physicists and solid state chemists. This book is based to a large extent on our experience of the crystal chemistry of copper oxides, which we have been studying in the laboratory for more than twelve years, but it also summarizes the main results which have been obtained for these compounds in the last five years relating to their spectacular superconducting properties. We have focused on the struc ture, chemical bonding and nonstoichiometry of these materials, bearing in mind that redox reactions are the key to the optimization of their supercon ducting properties, owing to the importance of the mixed valence of copper and its Jahn-Teller effect. We have also drawn on studies of extended defects by high-resolution electron microscopy and on their creation by ir radiation effects."

Despite the recent progress in developing various microanalytical tools of better spatial resolution and more sensitivity to chemical analyses for the study of various defects in metallic solids the Field-Ion Microscope (FIM) still remains the only instrument up to now to resolve single atoms in the surface of a metal. Fifteen years after Milller ) invented the FIM he was also the first to combine the FIM with a time-of-flight (ToF) mass spectrometer - the so-called Atom-Probe FlM - to identify the chemical nature of single atoms imaged in the FIM2). Originally the motivation to develop the ToF atom probe was to use this method to obtain some more fundamental understanding of field ionization and field evaporation, the most basic physical processes in field-ion microscopy. Even after the successful combination of a FIM with a ToF atom probe had been accomplished, the technique was rarely applied to metallurgical investigations since for a fairly long period only refractory metals such as tungsten, molybdenum, iridium, etc. could be imaged in the FIM. How ever, these metals do not playa very important role in metallurgy. Only when Turner et 3 al. ) substituted the conventional phosphorescent screen of the field-ion microscope with micro-channel electron multiplier arrays, termed micro channel plates, did it become possible to image in the FIM the less refractory metals like Fe, Cu, Ni and even AI."

For several years, the two parallel worlds of Molecular Conductors in one hand and Molecular Magnetism in the other have grown side by side, the former essentially based on radical organic molecules, the latter essentially based on the high spin properties of metal complexes. Over the last few years however, organometallic derivatives have started to play an increasingly important role in both worlds, and have in many ways contributed to open several passages between these two worlds. This volume recognizes this important emerging evolution of both research areas. It is not intended to give a comprehensive view of all possible organometallic materials, and polymers for example were not considered here. Rather we present a selection of the most recent research topics where organometallic derivatives were shown to play a crucial role in the setting of conducting and/or magnetic properties in crystalline materials. First, the role of organometallic anions in tet- thiafulvalenium-based molecular conductors is highlighted by Schlueter, while Kubo and Kato describe very recent ortho-metalated chelating ligands appended to the TTF core and their conducting salts. The combination of conducting and magnetic properties and the search for p-d interactions are analyzed in two comp- mentary contributions by Myazaki and Ouahab, while Valade focuses on the only class of metal bis(dithiolene) complexes to give rise to superconductive molecular materials, in association with organic as well as organometallic cations.

Over the past few years there has been a significant growth in the commercial application of a variety of processes which are all essentially based upon the very rapid heat treatment of powdered solid material in dilute gas suspensions. The objective of flash heating is usually to create a desirable product by means of physical and/or chemical transformations in the solid phase, usually with a high degree of control and with lower specific energy consumption than dense phase systems. Examples of successful flash reaction processing are to be found in the areas ofpyrometallurgy, mineral processing, plasma processing and, most recently, rapid prototyping. These developments have been based on, and have inspired, an expansion in fundamental research activities. As our understanding of flash reaction technology improves so does the need increase for the review of progress and the dissemination of accumulated knowl edge. Previous stocktaking on selected areas of flash reaction technology occurred in 1988 and can be found in the proceedings of three conferences held in that year: Flash Reaction Processes, Eds. D.G.C.Robertson, H.y'Sohn and N.J.Themelis, published by the Center for Pyrometallurgy, University of Missouri-Rolla, Rolla, MO 65401-0249; Production and Processing of Fine Particles, Ed. A.J .Plumpton, Pergamon Press, LeN 88-22755; High Temperature Dust-Laden Jets in Plasma Technology, Eds. O.P.Solonenko and A.I.Fedorchenko, VSP, Utrecht, ISBN 90- 6764-120-0."

Feldspar minerals make up 60% of the crust of the Earth. They are stable in the upper mantle, and are so abundant in the crust that they form the basis of the classification of igneous rocks. At the surface, feldspars weather to form clay minerals which are the most important mineral constituent of soils. The articles in this book review the chemical reactions of feldspars over the whole sweep of pressure and temperature regimes in the outer Earth, and describe the fundamental aspects of crystal structure which underlie their properties. The book covers intracrystalline reactions, such as order-disorder transformations and exsolution, and transfer of stable and radiogenic isotopes, which can be interpreted to provide insights into the thermal history of rocks. It is suitable for final year undergraduates or research workers.

Science and art of crystal growth represent an interdisciplinary activity based on fundamental principles of physics, chemistry and crystallography. Crystal growth has contributed over the years essentially to a widening of knowledge in its basic disciplines and has penetrated practically into all fields of experimental natural sciences. It has acted, more over, in a steadily increasing manner as a link between science and technology as can be seen best, for example, from the achievements in modern microelectronics. The aim of the course "Crystal Growth in Science and Technology" being to stress the interdisciplinary character of the subject, selected fundamental principles are reviewed in the following contributions and cross links between basic and applied aspects are illustrated. It is a very well-known fact that the intensive development of crystal growth has led to a progressive narrowing of interests in highly specialized directions which is in particular harmful to young research scientists. The organizers of the course did sincerely hope that the program would help to broaden up the horizon of the participants. It was equally their wish to contribute within the traditional spirit of the school of crystallography in Erice to the promotion of mutual understanding, personal friendship and future collaboration between all those who were present at the school.

Polytypic crystals of semiconductors, dielectrics and magnetic materials attract an increasing attention in science and technology. On one hand, the phenomenon of polyty pism is one of the fundamental problems of solid-state physics; its solution would make it possible to elucidate- the problem of the interconnection of different structures and intraatomic forces acting in crystals. On the other hand, the polytypic difference in crystals is most strongly expressed in electro-physical properties, which makes their application promising, mainly in semiconductor electronics. Thus, the difficulties of pro ducing modulated structures in polytypic crystals can be overcome since these crystals form a class of one-dimensional natural superlattices. At present it has become clear that polytypism in crystals and compounds is the rule rather than an exception and it is determined by the conditions of their synthesis. This phenomenon seems to be rather widespread in nature and fundamental for crystal forma tion. H polytypism was recently thought to be but a specific structural feature of a few substances such as SiC, ZnS, CdI , etc. , by now this phenomenon has been discovered in 2 v an increasing range of crystalline substances, for example, in silicon, diamond, AIIIB , VI AIIB , AIBVII compounds, in ternary semiconducting compounds, metals, silicates, perovskites, mica, organic crystals. The more accurately the structural studies are per formed, the greater is the number of crystals of various substances found to exhibit the phenomenon of polytypism. Recently, excellent surveys have systematized our knowledge of polytypism.

This series of books, which is published at the rate of about one per year, addresses fundamental problems in materials science. The contents cover a broad range of topics from small clusters of atoms to engineering materials and involve chemistry, physics, materials science, and engineering, with length scales ranging from Angstroms up to millimeters. The emphasis is on basic science rather than on applications. Each book focuses on a single area of current interest and brings together leading experts to give an up-to-date discussion of their work and the work of others. Each article contains enough references that the interested reader can access the relevant literature. Thanks are given to the Center for Fundamental Materials Research at Michigan State University for supporting this series. M.F. Thorpe, Series Editor E-mail: [email protected] East Lansing, Michigan, November 200 I v PREFACE The study of the atomic structure of crystalline materials began at the beginning of the twentieth century with the discovery by Max von Laue and by W.H. and W.L. Bragg that crystals diffract x-rays. At that time, even the existence of atoms was controversial.

Born and initially developed in various industrial laboratories, mainly in U.S.A. and Gennany, homogeneous phase catalytic carbon monoxide hydrogenation and alcohols and their derivatives carbonylation and homologation, have generally been considered and reviewed separately in the course of their 40 years history without concern for common aspects in the chemical transfonnations and in catalysis. Thanks to researchers of Japanese companies participating in the National C 1 Chemistry Project (1980-1987) the scientific and technical approaches in this field have been unified and applied in parallel, in the light of some common aspects of the chemical reactions and mechanisms. Now, at a moment when research seems becahned, a general presentation and discussion of the most recent topics might be an useful basis for further development of this chemistry. To delimit and simplify the discussion of the chemical aspects and the nature of the catalysts involved, the present review is limited to reactions employing homogeneous metal complexes for the direct conversion of syngas to oxygenates and to the hydrocarbonylation of these last to homologous derivatives. Since the previous practically contemporary reviews by Dombek [in Adv. Organomet. Chern. (1983)] on CO hydrogenation and by the present authors [in Asp.Homog.Catal.(Reidel Pu.l984)] on alcohol homologation fully cover the literature up to 1982, here we mainly refer to work done after 1982, and consider the cited reviews as covering the historical development of research in the 1940- 1980 period.

This book presents the third volume of a complete development of the new structural classification of minerals, which is based on the internal crystal structure, and is therefore its natural classification. Because of the large domain of the mineral kingdom, this work is divided in three volumes, in which the minerals are ordered from the structurally simple to the more complex.

Audience: This work will be of particular interest to teachers and research workers of in mineralogy, and in inorganic crystal structures in academia.

Today large numbers of geoscientists apply thermodynamic theory to solu tions of a variety of problems in earth and planetary sciences. For most problems in chemistry, the application of thermodynamics is direct and rewarding. Geoscientists, however, deal with complex inorganic and organic substances. The complexities in the nature of mineralogical substances arise due to their involved crystal structure and multicomponental character. As a result, thermochemical solutions of many geological-planetological problems should be attempted only with a clear understanding of the crystal-chemical and thermochemical character of each mineral. The subject of physical geochemistry deals with the elucidation and application of physico-chemical principles to geosciences. Thermodynamics of mineral phases and crystalline solutions form an integral part of it. Developments in mineralogic thermody namics in recent years have been very encouraging, but do not easily reach many geoscientists interested mainly in applications. This series is to provide geoscientists and planetary scientists with current information on the develop ments in thermodynamics of mineral systems, and also provide the active researcher in this rapidly developing field with a forum through which he can popularize the important conclusions of his work. In the first several volumes, we plan to publish original contributions (with an abundant supply of back ground material for the uninitiated reader) and thoughtful reviews from a number of researchers on mineralogic thermodynamics, on the application of thermochemistry to planetary phase equilibria (including meteorites), and on kinetics of geochemical reactions."

The history of the rare earths has entered its third century; trans uranium elements are now a half century old. Both the lanthanide and actinide ele- ments, 30 elements altogether, are f elements, meaninj that their metallic 2 1 1 electronic configurations are typically 6s 5d 4f" and 7s 6d 5f" respectively. To an elementary approximation as summarized in the 'average inorganic chemistry textbook, these configurations cause their chemistry to be described by the trivalent state accompanied by less interesting effects such as the lanthanide contraction. However, the discovery of divalent and tetravalent lanthanides and di- to seven-valent actinides hinted at the existence of more interesting although still classic solid-state and coor- dination chemistry. Metallic halides and chalcogenides and electron-poor cluster compounds have been the outgrowth of many synthetic efforts during the past 25 years or so. These days, one can say that the lan- thanides and actinides are not at all boring; the fascination arises from every element being an individual, having its own chemistry.

Nitrogen dioxide (N0 ) is notorious for its complex visible spectrum and has 2 frustrated many chemists and physicists. Despite their intense investigations the molecule still resists complete analysis of its spectrum. Because of the high density of lines, it is apparent that high-resolution measurements are essential to a thorough understanding of the spectrum. The major part of this book consists of an atlas, described in Chap. 2, of the absorption spectrum and the Stark modulation spectrum of N0 mea 2 sured using a cw dye laser. The narrow spectral width as well as the wide scan range of the dye laser made it possible to record the spectra contin uously over a wide range with Doppler-limited resolution. In the spectral range 16751-17885 em-I, about 13300 peaks have been observed in the absorption spectrum and their wave numbers, calibrated against Ar lines, are listed in the tables. The Stark modulation spectrum also shown provides useful information about the energy level structures complementary to that obtained from the absorption spectrum."

Cluster science studies the transition from atomic, and molecular physics or chemistry to the science and technology of condensed matter. Two main topics from this large field will be emphasized in this second volume of Atomic and Molecular Clusters. After an Introduction, Chap. 2 deals mainly with molecular clusters, how they react to positive or negative charges (Sect. 2.1 to 2.5), how they decompose and how they can be charged (Sect. 2.6 and 2.7), and how one can do chemistry with them (2.8 and 2.9). Clusters in contact with a macroscopic medium are treated in Chap. 3. It is from this domain that one can expect possible new applications of cluster science. The optical spectra of silver clusters in a dielectric medium are discussed in Sect. 3.1. Their properties have since long been used unknowingly to stain glass windows. Large clusters floating in an ambient pressure gas are called aerosols (Sect. 3.2). Their properties can be used to monitor air pollution. Development of a photographic film is due to supported silver clusters in a liquid environment (Sect. 3.3). Large semiconductor clusters, also called "quantum dots," have novel optical and electronic properties (Sect. 3.4). The optical properties of large clusters, in general, are reviewed in Sect. 3.5, and properties of clusters supported on clean surfaces are discussed in Sect. 3.6.

Scientists who have had the opportunity of being associated with Professor Egon T. Degens, to whom this Festschrift is devoted, have been influenced by his ideas on subjects as varied as: extraterrestrial organic matter, origin of life, evolution of organisms, isotope biogeochemistry down to more imminent ones such as the carbon cycle and its implications on climate. This variety is also reflected in the papers in the present volume contributed by colleagues who have known Egon or have worked with him. Egon Theodor Degens was born on April 16, 1928 at Inden, Germany and had his education in Bonn and Wiirzburg. After a stint at the Pennsylvania State University he returned to Wiirzburg to help set up one of the first organic geochemistry laboratories in the world. This laboratory was the breeding ground for some of the eminent organic geochemists at work today. Later, he joined the California Institute of Technology and began his work on stable carbon isotopes, and later on biogeochemical compounds in natural waters. From California he moved on to the east coast, which led to yet another productive phase at the Woods Hole Oceanographic Institution. He was instrumental in the pioneering work carried out by the Woods Hole scientists in the Black Sea which is the largest anoxic basin in the world, and in the Red Sea where the first hydrothermal ore deposits on the seafloor were discovered.

Assembling a program in bioinorganic chemistry that is scientifi cally relevant, well defined, and self-consistent is not an easy task. In this attempt we decided to consider zinc enzymes, copper oxidases, cytochromes and cytochrome oxidase. The choice is in part due to the great attention that the current specialized literature devotes to these topics, which are now debated among chemists, biochemists, biophysicists, etc .. We believe that hydration reactions, hydrolytic and oxidative processes have much in common from the point of view of the reaction mechanisms, the comprehension of which represents a frontier of science. For these reasons these topics have been the subject of the NATO-ASI held at San Miniato, Pisa, Italy, from May 28 to June 8, 1982. We hope we can transfer here the main conclusions of what (we believe) was a very stimulating scientific meeting. We would like to thank the local saving bank, Cassa di Risparmio di San Miniato, for helping in many ways. The financial contribution from the European Research Office of the US Army, and from the Bruker Spectrospin s.r.l., Italy, is also acknowledged. The National Science Foundation of the United States has provided a travel grant to one of the participants from the U.S.A. We are grateful to the NATO Scientific Affairs Division which provided a grant to finance this Institute."

The field of Physical Chemistry has developed through the application of theories and concepts developed by physicists to properties or processes of interest to chemists. Physicists, being principally concerned with the basic ideas, have generally restricted their attention to the simplest systems to which the concepts applied, and the task of applying the techniques and theories to the myriad substances and processes that comprise chemistry has been that of the physical chemists. The field of Solid State Chemistry has developed with a major impetus from the synthetic chemists who prepared unusual, novel materials with the principal guid ing ideas growing out of an understanding of crystal structure and crystal structure relationships. The novel materials that pour forth from this chemical cornucopia cry out for further characterization and interpretation. The major techniques for the characterization and interpretation of crystalline solids have been developed in the fields of Solid State Physics and Crystallography. Thus, the need arose for expanding the realm of Physical Chemistry from its traditional concern with molecules and their properties and reactions to include the physics and chemistry of crystalline solids. This book deals with the applications of crystallography, group theory and thermodynamics to problems dealing with non molecular crystalline solids."

Solid-State NMR is a branch of Nuclear Magnetic Resonance which is presently experiencing a phase of strongly increasing popularity. The most striking evidence is the large number of contributions from Solid-State Resonance at NMR meetings, approaching that ofliquid state resonance. Important progress can be observed in the areas of methodological developments and applications to organic and inorganic matter. One volume devoted to more or less one of each of these areas has been published in the preceding three issues. This volume can be considered an addendum to this series. Selected methods and applications of Solid-State NMR are featured in three chapters. The first one treats the recoupling of dipolar interactions in solids, which are averaged by fast sample rotation. Following an introduction to effective Hamiltonians and Floquet theory, different types of experiment such as rotary resonance, dipolar chemical shift correlation spectroscopy, rotational resonance and multipulse recoupling are treated in the powerful Floquet formalism. In the second chapter, the different approaches to line narrowing of quadrupolar nuclei are reviewed in a. consistent formulation of double resonance (DaR) and dynamic angle spinning (DAS). Practical aspects of probe design are considered as well as advanced 2D experiments, sensitivity enhancement techniques, and spinning sideband manipulations. The use of such techniques dramatically increases the number of nuclei which can be probed in high resolution NMR spectroscopy. The final chapter describes new experimental approaches and results of structural studies of noncrystalline solids."

1. A.-R. Grimmer, Berlin, FRG; B. Bl}mich, Aachen, FRG: Introduction to Solid-State NMR 2. F. Laupretre, Paris, France: High-Resolution 13C NMRInvestigations of Local Dynamics in Bulk Polymers at Temperatures Below andAbove the Glass-Transition Temperature 3. D. Raftery, Philadelphia, PA;B.F. Chmelka, Santa Barbara, CA: Xenon NMR Spectroscopy 4. G. Fleischer, Leipzig, FRG; F. Fujara, Mainz, FRG: NMR as a Generalized Incoherent Scattering Experiment 5. P. Bl}mler, B. Bl}mich, Mainz, FRG: NMR Imaging of Solids

In the last two decades low-dimensional (low-d) physics has matured into a major branch of science. Quite generally we may define a system with restricted dimensionality d as an object that is infinite only in one or two spatial directions (d = 1 and 2). Such a definition comprises isolated single chains or layers, but also fibres and thin layers (films) of varying but finite thickness. Clearly, a multitude of physical phenomena, notably in solid state physics, fall into these categories. As examples, we may mention: * Magnetic chains or layers (thin-film technology). * Metallic films (homogeneous or heterogeneous, crystalline, amorphous or microcristalline, etc.). * I-d or 2-d conductors and superconductors. * Intercalated systems. * 2-d electron gases (electrons on helium, semiconductor interfaces). * Surface layer problems (2-d melting of monolayers of noble gases on a substrate, surface problems in general). * Superfluid films of ~He or 'He. * Polymer physics. * Organic and inorganic chain conductors, superionic conductors. * I-d or 2-d molecular crystals and liquid crystals. * I-d or 2-d ferro- and antiferro electrics.