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This book describes all aspects of the physics of transition metal compounds, providing a comprehensive overview of this diverse class of solids. Set within a modern conceptual framework, this is an invaluable, up-to-date resource for graduate students, researchers and industrial practitioners in solid-state physics and chemistry, materials science, and inorganic chemistry.
With more than 40% new and revised materials, this second edition offers researchers and students in the field a comprehensive understanding of fundamental molecular properties amidst cutting-edge applications. Including ~70 Example-Boxes and summary notes, questions, exercises, problem sets, and illustrations in each chapter, this publication is also suitable for use as a textbook for advanced undergraduate and graduate students. Novel material is introduced in description of multi-orbital chemical bonding, spectroscopic and magnetic properties, methods of electronic structure calculation, and quantum-classical modeling for organometallic and metallobiochemical systems. This is an excellent reference for chemists, researchers and teachers, and advanced undergraduate and graduate students in inorganic, coordination, and organometallic chemistry.
With contributions by numerous experts
The structural phase transition is one of the most fundamental problems in solid state physics. Layered transition-metal dichalcogenides provide us with a most exciting area for the study of structural phase transitions that are associated with the charge density wave (CDW). A large variety of structural phase transitions, such as commensurate and incommensurate transitions, and the physical proper ties related to the formation of a CDW, have been an object of intense study made for many years by methods employing modem microscopic techniques. Rather recently, efforts have been devoted to the theoretical understanding of these experimental results. Thus, McMillan, for example, has developed an elegant phenomenological theory on the basis of the Landau free energy expansion. An extension of McMillan's theory has provided a successful understanding of the successive phase transitions observed in the IT- and 2H-compounds. In addition, a microscopic theory of lattice instability, lattice dynamics, and lattice distortion in the CDW state of the transition-metal dichalcogenides has been developed based on their electronic structures. As a result, the driving force of the CDW formation in the IT- and 2H-compounds has become clear. Furthermore, the effect of lattice fluctuations on the CDW transition and on the anomalous behavior of various physical properties has been made clear microscopically.
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.
There exists a large literature on the spectroscopic properties of copper(II) com- 9 pounds. This is due to the simplicity of the d electron configuration, the wide variety of stereochemistries that copper(II) compounds can adopt, and the f- xional geometric behavior that they sometimes exhibit [1]. The electronic and geometric properties of a molecule are inexorably linked and this is especially true with six-coordinate copper(II) compounds which are subject to a Jahn-T- ler effect.However,the spectral-structural correlations that are sometimes d- wn must often be viewed with caution as the information contained in a typical solution UV-Vis absorption spectrum of a copper(II) compound is limited. Meaningful spectral-structural correlations can be obtained in a related series of compounds where detailed spectroscopic data is available. In the fol- 4– lowing sections two such series are examined; the six-coordinate CuF and 6 2+ Cu(H O) ions doped as impurities in single crystal hosts.Using low tempera- 2 6 ture polarized optical spectroscopy and electron paramagnetic resonance, a very detailed picture can be drawn about the geometry of these ions in both their ground and excited electronic states. We then compare the spectrosco- cally determined structural data with that obtained from X-ray diffraction or EXAFS measurements.
This is a textbook of what is often called magnetochemistry. We take the point of view that magnetic phenomena are interesting because of what they tell us about chemical systems. Yet, we believe it is no longer tenable to write only about such subjects as distinguishing stereochemistry from the measurement of a magnetic susceptibility over a restricted temper ature region; that is, paramagnetism is so well-understood that little remains to explore which is of fundamental interest. The major purpose of this book is to direct chemists to some of the recent work of physicists, and in particular to a lengthy exposition of magnetic ordering phenomena. Chemists have long been interested in magnetic interactions in clusters, but many have shied away from long-range ordering phenomena. Now however more people are investigating magnetic behavior at temperatures in the liquid helium region, where ordering phenomena can scarcely be avoided. The emphasis is on complexes of the iron-series ions, for this is where most of the recent work, both experimental and theoretical, has been done. The discussion therefore is limited to insulating crystals; the nature of magnetism in metals and such materials as semiconductors is sufficiently different that a discussion of these substances is beyond our purposes. The book is directed more at the practical experimentalist than at the theoretician.
Electron paramagnetic resonance (epr) spectroscopy is a sensitive and versatile method of studying paramagnets, which is finding increasing use in chemistry, biochemistry, earth and materials sciences. The technique is treated both qualitatively and quantitatively, with a progressive increase in sophistication in each succeeding chapter. Following a general introductory chapter, the first half of the book deals with single unpaired electron systems and considers both metal and ligand Zeeman, hyperfine and quadrupole interactions. The simulation of these spectra is discussed, followed by the relationship between spin-Hamiltonian parameters and models of the electronic structures of paramagnets. The second half of the book treats multiple unpaired electron systems using the same philosophy. An introduction to the epr properties of cluster compounds and of extended exchanging systems is also given. There is a chapter on linewidths and lineshapes, and an extensive appendix containing much additional information. A wide-ranging library of simulated and experimental spectra is given, as well as graphical data which should aid spectrum interpretation. Each chapter contains key references and there is a substantial subject and keyword index. This book is designed to teach epr spectroscopy to students without any previous knowledge of the technique. However, it will also be extremely useful to researchers dealing with paramagnetic d transition metals.
Inorganic and Organometallic Transition Metal Complexes with Biological Molecules and Living Cells provides a complete overview of this important research area that is perfect for both newcomers and expert researchers in the field. Through concise chapters written and edited by esteemed experts, this book brings together a comprehensive treatment of the area previously only available through scattered, lengthy review articles in the literature. Advanced topics of research are covered, with particular focus on recent advances in the biological applications of transition metal complexes, including inorganic medicine, enzyme inhibitors, antiparasital agents, and biological imaging reagents. - Geared toward researchers and students who seek an introductory overview of the field, as well as researchers working in advanced areas - Focuses on the interactions of inorganic and organometallic transition metal complexes with biological molecules and live cells - Foscuses on the fundamentals and their potential therapeutic and diagnostic applications - Covers recent biological applications of transition metal complexes, such as anticancer drugs, enzyme inhibitors, bioconjugation agents, chemical biology tools, and bioimaging reagents
This book starts with the most elementary ideas of molecular orbital theory and leads the reader progressively to an understanding of the electronic structure, geometry and, in some cases, reactivity of transition metal complexes. The qualitative orbital approach, based on simple notions such as symmetry, overlap and electronegativity, is the focus of the presentation and a substantial part of the book is associated with the mechanics of the assembly of molecular orbital diagrams. The first chapter recalls the basis for electron counting in transition metal complexes. The main ligand fields (octahedral, square planar, tetrahedral, etc.) are studied in the second chapter and the structure of the "d block" is used to trace the relationships between the electronic structure and the geometry of the complexes. The third chapter studies the change in analysis when the ligands have pi-type interactions with the metal. All these ideas are then used in the fourth chapter to study a series of selected applications of varying complexity (e.g. structure and reactivity). The fifth chapter deals with the "isolobal analogy" which points out the resemblance between the molecular orbitals of inorganic and organic species and provides a bridge between these two subfields of chemistry. The last chapter is devoted to a presentation of basic Group Theory with applications to some of the complexes studied in the earlier chapters.