EPR Spectroscopy in Catalysis, by Sabine Van Doorslaer und Damien M. Murphy Radicals in Flavoproteins, by Erik Schleicher und Stefan Weber EPR Spectroscopy in Polymer Science, by Dariush Hinderberger EPR in Protein Science, by Intrinsically Disordered Proteins, by Malte Drescher Site-Directed Spin Labeling of Membrane Proteins, by Enrica Bordignon Structure and Dynamics of Nucleic Acids, by Ivan Krsti, Burkhard Endeward, Dominik Margraf, Andriy Marko und Thomas F Prisner New Directions in Electron Paramagnetic Resonance Spectroscopy on Molecular Nanomagnets, by J. van Slageren"

These proceedings report the lectures and seminars presented at the NATO Advanced Study Institute on "Optical Properties of Ions in Solids," held at Erice, Italy, June 6-21, 1974. The Institute was the first activity of the International School of Atomic and Molecular Spectroscopy of the "Ettore Majorana" Centre for Scientific Culture. The Institute consisted of a series of lectures on optical properties of ions in solids that, starting at a fundamental level, finally reached the current level of research. The sequence of lectures and the organization of the material taught were in keeping with a didactical presentation. In essence the Institute had the two-fold purpose of organizing what was known on the subject, and updating the knowledge in the field. Fif'teen series of lectures for a total of 44 hours were given. Five one-hour seminars and five twenty-minute seminars were presented. A total of 57 participants came from 40 laboratories in the following countries: Belgium, Canada, France, Germany, Ireland, Israel, Italy, Netherlands; Polatid, Romania, Switzerland, the United Ki gdom, and the United States. The secretaries of the Institute were: D. Pacheco for the scientific aspects and A. La Francesca for the administrative aspects of the meeting. These proceedings report the lectures, the one-hour seminars (abstracts only) and the twenty-minute- seminars (titles only). The proceedings report also the contributions sent by Prof. K. Rebane and Dr. L. A. Rebane who, unfortunately, were not able to come.

In the summer of 1972, I had the privilege and responsibility of organizing a Gordon Conference on the "High-Energy Spectroscopy of Solids." The Thursday evening session focused on future directions for high-energy spectroscopy. The possibilities associated with synchrotron radiation for future research became a central issue. I was asked to choose the members of the panel and chair the session. Although all five members of the panel went on to have distinguished careers using synchrotron radiation, at the time some of them were skeptical about the future role of synchrotron radiation sources in high-energy photon spectroscopy. The discussion became heated, and many members of the audience spoke, both pro and con. One member of the panel produced a detailed argument that synchrotron radiation would never rival standard X-ray tubes. We found out that there were estimates for properties of synchrotrons that differed by orders of magnitude from those of X-ray tubes. That much uncertainty was expressed at a meeting that took place less than twenty years ago. It is hard to believe that, even though at that time synchrotron radiation was already being used for photoemission studies of solids and surfaces and intershell excitations in solids, the potential impact and importance of this area was not fully realized even by the experts. Today synchrotron radiation is one of the primary tools for studying surfaces, and synchrotron radiation has affected many other areas of condensed-matter physics---even superconductivity.

Crystal defects can no longer be thought of as a scientific curiosity, but must be considered an important aspect of solid-state science. This is largely because many of the more interesting properties of crystalline solids are disproportionately dominated by effects due to a tiny concentration of imperfections in an otherwise perfect lattice. The physics of such lattice defects is not only of significance in a great variety of applications, but is also interesting in its own right. Thus, an extensive science of point defects and dislocations has been constructed during the past two and a half decades. Stimulated by the technological and scientific interest in plasticity, there have appeared in recent years rather a large number of books dealing with dislocations; in the case of point defects, however, only very few broad and extensive treatments have been published. Thus, there are few compre hensive, tutorial sources for the scientist or engineer whose research ac tivities are affected by point defect phenomena, or who might wish to enter the field. It is partially to fill this need that the present treatise aims.

This book focuses on the metallic Nano- and Micro-materials (NMMs) fabricated by physical techniques such as atomic diffusion. A new technology for fabricating NMMs by atomic diffusion is presented. Two kinds of atomic diffusion are treated; one is a phenomenon caused by electron flow in high density and called electromigration and the other is stress migration which depends on a gradient of hydrostatic stress in a material.

In three parts, the book describes the theory of atomic diffusion, the evaluation of physical properties and the treatment and applications of metallic NNMS. The new methods such as atomic diffusion are expected are expected to be crucial for the fabrication of NNMs in the future and to partially replace methods based on chemical reactions.

Arbeitshypothesen sind revidierbar, deklarierten Wahrheiten nicht, sie verkalken zum System; Arbeitshypothesen passen sich den Menschen an, den deklarierten Wahrheiten wird der Mensch angepajJt; die ersten kann mann verwerfen, von den anderen wird man verworfen. FRIEDRICH DORRBNMATI, Nachgedanken Working hypotheses can be revised,' declared truths cannot-they calcify into dogma. Working hypotheses adapt to people-people adapt to declared truths. One can reject the first but be rejected by the latter. The concept of electron crystallography, i.e., the quantitative use of electron diffraction intensities to solve crystal structures, is by no means new. Based on extensive pioneering efforts on organic and inorganic substances, two major works on electron diffraction structure analysis (or "electronography" as it was then known in Moscow) appeared in English translation during the 19608. These books are B. K. Vainshtein, Strukturnaya Elektronografiya (Structure Analysis by Electron Diffrac- tion, translated by E. Feigl andJ. A. Spink, Pergamon Press, Oxford, 1964), and B. B.

Both experimental and theoretical investigations make it clear that mesoscale materials, that is, materials at scales intermediate between atomic and bulk matter, do not always behave in ways predicted by conventional theories of shock compression. At these scales, shock waves interact with local material properties and microstructure to produce a hierarchy of dissipative structures such as inelastic deformation fields, randomly distributed lattice defects, and residual stresses. A macroscopically steady planar shock wave is neither plane nor steady at the mesoscale. The chapters in this book examine the assumptions underlying our understanding of shock phenomena and present new measurements, calculations, and theories that challenge these assumptions. They address such questions as: - What are the experimental data on mesoscale effects of shocks, and what are the implications? - Can one formulate new mesoscale theories of shock dynamics? - How would new mesoscale theories affect our understanding of shock-induced phase transitions or fracture? - What new computational models will be needed for investigating mesoscale shocks?

The functionalization of surfaces on the nanoscale is one of the most fascinating and at the same time challenging topics in science. It is the key to tailoring catalysts, sensors, or devices for solar energy conversion, whose functional principle is based on the interaction of an active solid surface with another (liquid or gaseous) phase. As an example, planar transition metal complexes adsorbed on solid supports are promising candidates for novel heterogeneous catalysts. An important feature of these catalysts, compared to supported metal clusters, is the fact that the active sites, i. e. , the coordinated metal centers with their vacant axial coordination sites, are well de?ned and uniform. Metalloporphyrinoids are particularly suitable in this respect because they combine a structure forming element-the rigid molecular frame, which often induces long range order-with an active site, the coordinated metal ion. Its planar coordination environment leaves two axial coordination sites available for additional ligands. If adsorbed on a surface, one of these axial sites is occupied by the underlying substrate. The resulting electronic interaction with the surface can be used to tailor the electronic structure and thereby the reactivity of the metal center. The remaining site is free for the attachment of molecules (sensor functionality) and/or operates as a reaction center (single-site catalysis). Prototype examples are omnipresent in nature, where in particular metallo-tetrapyrrols play a decisive role in important biological processes, with the most prominent examples being iron porphyrins in heme, magnesium porphyrins in chlorophyll, and cobalt corrin in vitamin B12.

The book is designed for end users in the field of digital imaging, who wish to update their skills and understanding with the latest techniques in image analysis. The book emphasizes the conceptual framework of image analysis and the effective use of image processing tools. It uses applications in a variety of fields to demonstrate and consolidate both specific and general concepts, and to build intuition, insight and understanding. Although the chapters are essentially self-contained they reference other chapters to form an integrated whole. Each chapter employs a pedagogical approach to ensure conceptual learning before introducing specific techniques and "tricks of the trade". The book concentrates on a number of current research applications, and will present a detailed approach to each while emphasizing the applicability of techniques to other problems. The field of topics is wide, ranging from compressive (non-uniform) sampling in MRI, through automated retinal vessel analysis to 3-D ultrasound imaging and more. The book is amply illustrated with figures and applicable medical images. The reader will learn the techniques which experts in the field are currently employing and testing to solve particular research problems, and how they may be applied to other problems.

This NATO Advanced Study Institute, held in Geilo between March 29th and April 9th 1981, was the sixth in a series devoted to the subject of phase transitions and instabilities. The present institute was intended to provide a forum for discussion of the importance of nonlinear phenomena associated with instabilities in systems as seemingly disparate as ferroelectrics and rotating buckets of oil. Ten years ago, at the first Geilo school, the report of a central peak in the fluctuation spectrum of SrTi0 close to its 3 106 K structural phase transition demonstrated that the simple soft-mode theory of such transitions was incomplete. The missing ingredient was the essential nonlinearity of the system. Parti cipants at this year's Geilo school heard assessments of a decade of experimental and theoretical effort which has been expended to elucidate the nature of this nonlinearity. The importance of order ed clusters and the walls which bound them was stressed in this con text. A specific type of wall, the soliton, was discussed by a number of speakers. New experimental results which purport to demonstrate the existence of solitons in a one-dimensional ferromagnet were presented. A detailed discussion was given of the role of solitons in transport phenomena in driven multistable systems, typified by a sine-Gordon chain."

This NATO Advanced Study Institute held at Gei10, Norway, April 16th-27th 1979, was the fifth in a series devoted to the subject of phase transitions and instabilities. The application to NATO for the funding of this ASI contained the following para graphs: "Traditionally one has made a clear distinction between solids and liquids in terms of positional order, one being long-ranged and the other at most short-ranged. In recent years experiments have revealed a much more faceted picture and a less sharp distinction between solids and liquids. As an example one now has 3-dimensiona1 (3-D) liquids with 1-D density waves and 3-D solids with 1-D-1iquid molecular chains. The subsystems have the common feature of 10w dimensional systems: a strong tendency for fluctuations to appear. Although the connection between fluctuations and dimensionality, and the suppression of long-range order by fluctuations, was pointed out as early as 1935 by Peier1s and by Landau, it is in the last five years or so that theoretical work has gained momentum. This development of understanding started ten years ago, however, much inspired by the experimental work on 2-D spin systems."

The diffusion or migration of atoms in matter, of whatever form, is a basic consequence of the existence of atoms. In metals, atomic diffusion has a well established position of importance as it is recognized that there are few metallurgical processes which do not embody the diffusion of one or more of the constituents. As regards semiconductors any thermal annealing treatment involves atomic diffusion. In semiconductor technology diffusion processes provide a vital and basic means of fabricating doped structures. Notwithstanding the importance of diffusion in the preparative processes of semiconductor structures and samples, the diffusion based aspects have acquired an empirical outlook verging almost on alchemy. The first attempt to present a systematic account of semiconductor diffusion processes was made by Boltaks [11 in 1961. During the decade since Boltaks' book appeared much work germane to understanding the atomic mechanisms responsible for diffusion in semiconductors has been published. The object of the present book is to give an account of, and to consolidate, present knowledge of semiconductor diffusion in terms of basic concepts of atomic migration in crystalline lattices. To this end, exhaustive compilations of empirical data have been avoided as these are available elsewhere [2, 31 : attention has been limited to considering evidence capable of yielding insight into the physical processes concerned in atomic diffusion.

This is the sixth volume of a well-established and popular series in which expert practitioners discuss topical aspects of light scattering in solids. This volume discusses recent results of Raman spectroscopy of high Tc superconductors, organic polymers, rare earth compounds, semimagnetic superconductors, and silver halides, as well as developments in the rapidly growing field of time-resolved Raman spectroscopy. Emphasis is placed on obtaining information about elementary excitations, the basic properties of materials, and the use of Raman spectroscopy as an analytical tool. This volume may be regarded as an encyclopedia of condensed matter physics from the viewpoint of the Raman spectroscopist. It will be useful to advanced students and to all researchers who apply Raman spectroscopy in their work.

Application of NMR and Molecular Docking in Structure-Based Drug Discovery, by Jaime L. Stark and Robert Powers NMR as a Unique Tool in Assessment and Complex Determination of Weak Protein-Protein Interactions, by Olga Vinogradova and Jun Qin The Use of Residual Dipolar Coupling in Studying Proteins by NMR, by Kang Chen und Nico Tjandra NMR Studies of Metalloproteins, by Hongyan Li and Hongzhe Sun Recent Developments in 15N NMR Relaxation Studies that Probe Protein Backbone Dynamics, by Rieko Ishima Contemporary Methods in Structure Determination of Membrane Proteins by Solution NMR, by Tabussom Qureshi and Natalie K. Goto Protein Structure Determination by Solid-State NMR, by Xin Zhao Dynamic Nuclear Polarization: New Methodology and Applications, by Kong Hung Sze, Qinglin Wu, Ho Sum Tse and Guang Zhu

In the course of the development of surface science, advances have been identified with the introduction of new diagnostic probes for analytical characterization of the adsorbates and microscopic structure of surfaces and interfaces. Among the most recently de veloped techniques, and one around which a storm of controversy has developed, is what has now been earmarked as surface enhanced Raman scattering (SERS). Within this phenomenon, molecules adsorbed onto metal surfaces under certain conditions exhibit an anomalously large interaction cross section for the Raman effect. This makes it possible to observe the detailed vibrational signature of the adsorbate in the ambient phase with an energy resolution much higher than that which is presently available in electron energy loss spectroscopy and when the surface is in contact with a much larger amount of material than that which can be tolerated in infrared absorption experiments. The ability to perform vibrational spectroscopy under these conditions would lead to a new understanding about the chemical identity, geome try, and bonding of adsorbed material at a level previously unacces sible. It is for these reasons that the last few years have brought an explosion of activity surrounding the exploitation of SERS. The search for the origines) of the anomalous enhancement has given rise to a research sub-activity of its own. Efforts to explain the en hancement have led to an increased understanding of the whole range of phenomena associated with the interaction of photons with adsor bates and metal surfaces."

The importance of real space imaging and spatially-resolved spectroscopy in many of the most significant problems of surface and interface behaviour is almost self evident. To join the expertise of the tradi tional surface scientist with that of the electron microscopist has however been a slow and difficult process. In the past few years remarkable progress has been achieved, including the development of new techniques of scanning transmission and reflection imaging as well as low energy microscopy, all carried out in greatly improved vacuum conditions. Most astonishing of all has been the advent of the scanning tunneling electron microscope providing atomic resolution in a manner readily compatible with most surface science diagnostic procedures. The problem of beam damage, though often serious, is increasingly well understood so that we can assess the reliability and usefulness of the results which can now be obtained in catalysis studies and a wide range of surface science applications. These new developments and many others in more established surface techniques are all described in this book, based on lectures given at a NATO Advanced Study Institute held in Erice, Sicily, at Easter 1987. It is regretted that a few lectures on low energy electron diffraction and channeling effects could not be included. Fifteen lecturers from seven different Countries and 67 students from 23 Countries and a wide variety of backgrounds attended the school.

here exists a gap in the present literature on quantum mechanics T and its application to solids. It has been difficult to find an intro ductory textbook which could take a student from the elementary quan tum mechanical ideas of the single-particle Schrodinger equations, through the formalism and new physical concepts of many-body theory, to the level where the student would be equipped to read the scientific literature and specialized books on specific topics. The present book, which I believe fills this gap, grew out of two courses which I have given for a number of years at the University of Cambridge: "Advanced Quan tum Mechanics," covering the quantization of fields, representations, and creation and annihilation operators, and "Many Body Theory," on the application of quantum field theory to solids. The first course is a final-year undergraduate physics course while the second is a joint first and fourth-year undergraduate math year postgraduate physics course ematics course. In an American context this would closely correspond to a graduate course at the masters level. In writing this book I have tried to stress the physical aspects of the mathematics preferring where possible to introduce a technique by using a simple illustrative example rather than develop a purely formal treat ment. In order to do this I have assumed a certain familiarity with solid state physics on the level of a normal undergraduate course, but the book should also be useful to those without such a background."

During the preparation of this compilation, many people contributed; the compilers wish to thank all of them. In particular they appreciate the efforts of V. Gilbertson, the manuscript typist, and those of K. C. Bregand, J. A. Kiley, and W. H. McPherson, who gave editorial assistance. They would like to thank Dr. J. R. Schwartz for his cooperation and encouragement. In addition, they extend their grati tude to Dr. L. Wilson of the Air Force Weapons Laboratory, who gave the initial impetus to this project. v Contents I. I ntroduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1 . . . . . . . . . . . . . . . . 11. Organization ofthe Spectroscopic Table. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2 Methods of Production and Experimental Technique . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2 Band Systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2 Spectroscopic Constants . '. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3 Perturbations and General Information. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4 Bibliography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4 111. Notation and Notational Conversion Formulas. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5 IV. Conclusions on the Availability of Spectroscopic Information. . . . . . . . . . . . . . . . . . . . . . 8 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11 Spectroscopic Information Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13 A . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19 B 55 C 103 D 167 E 169 F 173 185 G H 191 I 265 K 321 337 L M 351 N 359 o 435 P 463 R 487 S 495 T 541 U 567 V 569 571 X y . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 579 Z 583 vii 1. INTRODUCTION In recent years, the need for a complete collection of information rele vant to diatomic moleeules has become evident. Several excellent collections of this type of information have been available for many years (Refs. 1-3); however, the state of our collective knowledge has been considerably expanded since their publication."

The extensive use of low-energy accelerators in non-nuclear physics has now reached the stage where these activities are recognized as a natural field of investigation. Many other areas in physics and chemistry have undergone similarly spectacular development: beam foil spectroscopy in atomic physics, studies in atomic collisions, materials implantation, defects creation, nuclear microanalysis, and so on. Now, this most recent activity by itself and in its evident connec tion with the others has brought a new impetus to both the funda mental and the applied aspects of materials science. A summer school on "Material Characterization Using Ion Beams" has resulted from these developments and the realization that the use of ion beams is not restricted to accelerators but covers a wide energy range in the developing technology. The idea of the ion beam as a common denominator of many act1v1t1es dealing with surface and near-surface characterization was enthu siastically received by many scientists and a school on this subject received the positive endorsement of NATO. The Advanced Study Institute on Materials Science has assumed for us the status of an "institution" leading to better contact among the many laboratories engaged in this field. The fourth Institute in this series was held in Aleria, Corsica, between August 22 and September 12, 1976."

This volume comprised the proceedings of a NATO Advanced Study Institute held in Geilo, Norway between 29 March and 9 April 1987. Al though the principal support for the meeting was provided by the NATO Cornrni ttee for Scientific Affairs, a number of additional sponsors also contributed. Additional funds were received from: Institutt for Energiteknikk (Norway) The Norwegian Research Council for Science and Humanities NORDITA (Denmark) VISTA (Norway) The organizing cornrni ttee would like to take this opportunity to thank all sponsors for their help in promoting an exciting and rewarding meeting. This Study Institute was the ninth of a series of meetings held in Geilo on subjects related to phase transitions and was a natural successor to the 1985 meeting on Scaling Phenomena in Disordered Systems. Many of the subjects discussed at the latter meeting were revisited in 1987, with time dependence as an added feature. Often the common theme was the concept of fractals first introduced into statistical physics some six years ago. However, by no means all disordered systems can be forced into a fractal framework, and many of the lectures reinforced this lesson.

I am happy indeed to write a foreword to this book. Since it was founded, the A. F. Ioffe Institute in Leningrad has been in the forefront of semiconductor research. I visited it in 1934, and vividly remember A . F. Ioffe himself and J. Frenkel and their kindness to me, and to others attending the meeting to celebrate the hundredth anniversary of Mendeleev. In the last years my own work on non-crystalline semiconductors has been strongly influenced by the work of B. T. Kolomiets and his co-workers. The English-speaking world should know the great Institute better, and this book will, I am sure, help this to happen. Nevill Mott Cambridge, June 1985 v Contents INTRODUCTORY PART Abram Fyodorovich Ioffe (29th October 1880 - 14th October 1960) 3 V. M. Tuchkevich and V. Ya. Frenkel Semiconductors: A New Material for Electrical Engineering 11 A. F. Ioffe EXPERIMENTAL PART Photovoltaic Solar Energy Conversion 19 Zh. 1. Alferov New Optical Methods in Semiconductor Research 37 B. P. Zakharchenya Reemission, Quantum Efficiency and Lifetimes of Radiative Recombination in A3BS Semiconductors and Heterostructures 53 D. Z. Garbuzov Interacting Excitons in Germanium and Silicon 87 P. D. Altukhov, V. M. Asnin and A. A. Rogachev Liquid Semiconductors 129 A. R. Regel and A. A. Andreev Chalcogenide Vitreous Semiconductors 143 B. T. Kolomiets, E. A. Lebedev, V. M. Lyubin, T. F. Mazets and T. N. Mamontova vii viii CONTENTS Electron and Hole Recombination in Narrow Gap Semiconductors 169 B. L. Gelmont and V. I."

This book presents an account of the course "Disordered Solids: Structures and Processes" held in Erice, Italy, from June 15 to 29, 1987. This meeting was organized by the International School of Atomic and Molecular Spectroscopy of the "Ettore Majorana" Centre for Scientific Culture. The objective of this course was to present the advances in physical modelling, mathematical formalism and experimental techniques relevant to the interpretation of the structures of disordered solids and of the physical processes occurring therein. Traditional solid-state physics treats solids as perfect crystals and takes great advantage of their symmetry, by means of such mathematical formalisms as the reciprocal lattice, the Brillouin zone, and the powerful tools of group theory. Even if in reality no solid is a perfect crystal, this theoretical approach has been of great usefulness in describing solids: deviations from perfect order have been treated as perturbations of the ideal model. A new situation arises with truly disordered solids where any vestige of long range order has disappeared. The basic problem is that of describing these systems and gaining a scientific understanding of their physical properties without the mathematical formalism of traditional solid state physics. While some of the old approaches may occasionally remain valid (e. g. chemical bonding approach for amorphous solids), the old ways will not do. Disorder is not a perturbation: with disorder, something basically new may be expected to appear."