As semiconductor manufacturers implement copper conductors in advanced interconnect schemes, research and development efforts shift toward the selection of an insulator that can take maximum advantage of the lower power and faster signal propagation allowed by copper interconnects. One of the main challenges to integrating a low-dielectric constant (low-kappa) insulator as a replacement for silicon dioxide is the behavior of such materials during the chemical-mechanical planarization (CMP) process used in Damascene patterning. Low-kappa dielectrics tend to be softer and less chemically reactive than silicon dioxide, providing significant challenges to successful removal and planarization of such materials. The focus of this book is to merge the complex CMP models and mechanisms that have evolved in the past decade with recent experimental results with copper and low-kappa CMP to develop a comprehensive mechanism for low- and high-removal-rate processes. The result is a more in-depth look into the fundamental reaction kinetics that alter, selectively consume, and ultimately planarize a multi-material structure during Damascene patterning.

Quantum Simulations of Materials and Biological Systems features contributions from leading world experts in the fields of density functional theory (DFT) and its applications to material and biological systems. The recent developments of correlation functionals, implementations of Time-dependent algorithm into DFTB+ method are presented. The applications of DFT method to large materials and biological systems such as understanding of optical and electronic properties of nanoparticles, X-ray structure refinement of proteins, the catalytic process of enzymes and photochemistry of phytochromes are detailed. In addition, the book reviews the recent developments of methods for protein design and engineering, as well as ligand-based drug design. Some insightful information about the 2011 International Symposium on Computational Sciences is also provided. Quantum Simulations of Materials and Biological Systems is aimed at faculties and researchers in the fields of computational physics, chemistry and biology, as well as at the biotech and pharmaceutical industries.

This monograph describes and discusses the properties of heterogeneous materials, including conductivity, elastic moduli, and dielectrical constant. The book outlines typical experimental methods, and compares the experimental data and the theoretical predictions. This multidisciplinary book will appeal to applied physicists, materials scientists, chemical and mechanical engineers, chemists, and applied mathematicians.

This volume contains most of the invited lectures of the 2nd Structural Chemistry Indaba on "Molecular Interactions," held at Skukuza, Kruger Park, South Africa, August 3- 8, 1997. While the 1995 conference concentrated more on the principles underlying molecular modeling, like the existence of a molecular shape, this conference centers on molecular interactions or, more generally, on molecules in environments. Unfortunately, it was impossible, for various reasons, to unite all invited lectures in this volume, but nevertheless this collection contains contributions ranging from the fundamental quantum mechanical theory to recent research on organometallic crystals. For a summary, I would like to refer the reader to the introductory chapter by S.O. Sommerer, based on his concluding remarks at the conference. WemerGans for the editors v CONTENTS Intermolecular Interactions ...S. O. Sommerer Intermolecular Bonding ...3 1. C. A. Boeyens Chemical Reactions in the Framework of Single Quantum Systems ...9 A. Amann The Molecule and Its Environment ...25 ...B. T. Sutcliffe Dynamic Aspects of Intermolecular Interactions ...49 ...1. F. Ogilvie Atomic Interactions and the Charge Density ...5 7 ...T. Koritsanszky 71 Cyclometallation of Alkylphosphines M. T. Benson and T. R. Cundari C-H-. *0 Hydrogen Bonds in Organometallic Crystals 83 D. Braga and F. Grepioni The Importance of Intra-and Intermolecular Weak Bonds in Transition Metal Coordination Compounds ...97 P. Comba Relationships between Experiment and Theory in the Study of Intermolecular Interactions ...111 ...

The XII Max Born Symposium has a special character. It was held in honour th of Jan Lopusza nski on the occasion of his 75 birthday. As a rule the Max Born Symposia organized by the Institute of Theoretical Physics at the University of Wroc law were devoted to well-de ned subjects of contemporary interest. This time, however, the organizers decided to make an exception. Lopusza nski's in?uence on and contribution to the development of th- retical physics at Wrocla w University is highly appreciable. His personality and scienti c achievements gave him authority which he used to the best - vantage of the Institute. In fact we still pro t from his knowledge, experience and judgment. Lopusza nski's scienti c activity extended over about half a century. He successfully participated in research on the most important and fascinating issues of theoretical physics. During his scienti c career he met and made friends with many outstanding physicists who shaped theoretical physics to the present form. For this reason, as well as the coincidence of the approaching end of the century, we thought that it would be interesting and instructive to give the symposium a retrospective character. We decided to trust the speakers' judgment and intuition for the choice of subjects for their talks. We just asked them to give the audience the important message based on their knowledge and experience.

Predicting thermodynamic quantities for chemically realistic systems on the basis of atomistic calculations is still, even today, a nontrivial task. Nonetheless, accurate treatment of inter-particle interactions, in terms of quantum chemical first principles methods, is a prerequisite for many applications, because of the complexity of both reactants and solvents in modern molecular sciences. Currently, a straightforward calculation of thermodynamic properties from these methods is only possible for high-temperature and low- density systems. Although the enthalpy of a system can often be predicted to a good level of precision with this ideal gas approach, calculating the entropy contribution to the free energy is problematic, especially as the density of the system increases. This thesis contains a compact and coherent introduction of basic theoretical features. The foundations are then laid for the development of approaches suitable for calculation of condensed phase entropies on the basis of well-established quantum chemical methods. The main emphasis of this work is on realistic systems in solution, which is the most important environment for chemical synthesis. The presented results demonstrate how isolated molecular concepts typically employed in modern quantum chemistry can be extended for the accurate determination of thermodynamic properties by means of scale- transferring approaches.

Time-dependent density functional response theory for electronic chiroptical properties of chiral molecules; by Jochen Autschbach, Lucia Nitsch Velasquez, and Mark Rudolph

*

Chiroptical Properties of Charge-Transfer Compounds; by Yoshihisa Inoue, Tadashi Mori

*

G-C content independent long-range charge transfer through DNA; by Tetsuro Majima

*

Induced chirality in porphiryn aggregates: the role of weak and strong interactions; by Roberto Purrello

*

Vibrational circular dichroism spectroscopy of chiral molecules in solution; by Yunjie Xu

*

Magneto-electric properties of self-assembled monolayers of chiral molecules; by Zeev Vager and Ron Naaman

*

Theory of adsorption induced chirality and electron transfer through chiral systems; by Spiros Skourtis and David Beratan

*

Chiral-selective surface chemistry induced by spin-polarized secondary electrons; by Richard Rosenberg"

Hydrogen Bonding New Insights is an extensive text which takes numerous examples from experimental studies and uses these to illustrate theoretical investigations to allow a greater understanding of hydrogen bonding phenomenon. The most important topics in recent studies are considered including:

Intra-molecular H-bonds

Differences between H-bond and van der Waals interactions from one side and covalent bonds from the other

Bader theory to analyze H-bonding

Influence of weak H-bonds upon structure and function of biological molecules

H-bonds in crystal structures

With contributions from some of the foremost experts in this field this volume provides an invaluable resource for all members of the academic community looking for a comprehensive text on hydrogen bonding. It will be of particular interest to physical and theoretical chemists, spectroscopists, crystallographers and those involved with chemical physics."

Over the past 40 years, Rotational Isomeric State (RIS) models for hundreds of polymer structures have been developed. The RIS approach is now available in several software packages. The user is often faced with the time-consuming task of finding appropriate RIS parameters from the literature. This book aims at easing this step by providing a comprehensive overview of the models available. It reviews the literature from the first applications of RIS models to the end of 1994, comprises synthetic as well as naturally orccuring macromolecules, and tabulates all the pertinent features of published models. It will help readers, even when not very familiar with the method, to take advantage of this computationally efficient way of assessing the conformational properties of macromolecular systems.

1. R.G. Pearson Chemical Hardness - An Historical Introduction 2. P.K. Chattaraj Density Functional Theory of Chemical Hardness 3. J.L. Gazqu z Hardness and Softness in Density Functional Theory 4. L. Komorowski Hardness Indices for Free and Bonded Atoms 5. N.H. March The Ground-State Energy of Atomic and Molecular Ions and Its Variation with the Number of Elections 6. K. Sen Isoelectronic Changes in energy, Electronegativity, and Hardness in Atoms via the Calculations of 7. P. Politzer, J.S. Murray, M.E. Grice Charge Capacities and Shell Structures of Atoms 8. R. F. Nalewajski The Hardness Based Molecular Charge Sensitivities and Their Use in the Theory of Chemical Reactivity 9. B.G. Baekelandt, R. A. Schoonheydt, W.J. Mortier The EEM Approach to Chemical Hardness in Molecules and Solids: Fundamentals and Applications 10. J.A. Alonso, L. C. Balbas Hardness of Metallic Clusters

High-throughput screening and combinatorial chemistry are two of the most potent weapons ever to have been used in the discovery of new drugs. At a stroke, it seems to be possible to synthesise more molecules in a month than have previously been made in the whole of the distinguished history of organic chemistry, Furthermore, all the molecules can be screened in the same short period. However, like any weapons of immense power, these techniques must be used with care, to achieve maximum impact. The costs of implementing and running high-throughput screening and combinatorial chemistry are high, as large dedicated facilities must be built and staffed. In addition, the sheer number of chemical leads generated may overwhelm the lead optimisation teams in a hail of friendly fire. Mother nature has not entirely surrendered, as the number of building blocks that could be used to build libraries would require more atoms than there are in the universe. In addition, the progress made by the Human Genome Project has uncovered many proteins with different functions but related binding sites, creating issues of selectivity. Advances in the new field of pharmacogenomics will produce more of these challenges. There is a real need to make hi- throughput screening and combinatorial chemistry into 'smart' weapons, so that their power is not dissipated. That is the challenge for modellers, computational chemists, cheminformaticians and IT experts. In this book, we have broken down this grand challenge into key tasks.

1. G. Engelhardt, H. Koller, Stuttgart, FRG: 29Si NMR of Inorganic Solids 2. H. Pfeifer, Leizpig, FRG: NMR of Solid Surfaces 3. A. Sebald, Bayreuth, FRG: MAS and CP/MAS NMR of Less Common Spin-1/2 Nuclei 4. C. J{ger, Mainz, FRG: Satellite Transition Spectroscopy of Quadrupolar Nuclei 5. D. Brinkmann, M. Mali, Z}rich, CH: NMR-NQR Studies of High-Temperature Superconductors

In 1965 a book by P. Bartlett appeared under the title "The Nonclassical Ions" 1). The book is a collection of papers reprinted from various journals. The many reviews that have appeared since 2-22) are either antiquated (the book published in 1972 12) covers the literature mainly before 1968) or relatively biased (e.g., 3.4,10" on brief 2, 7,11). This review attempts to discuss the various points of view on the "nonclassical" carbocations. The main point is to establish the relative role of "nonclassical" and "classical" ions in various chemical processes. The author has followed P. Bartlett's advice 1) that when setting forth the achievements of the human mind one should see how we came to the modern understanding of a given problem (" ... how we know what we know"). The theory of "nonclassical" ions offers an explanation of many unique chemical, stereochemical and kinetic peculiarities of bicyclic compounds. It has expanded our knowledge on chemical bonds in carbocations by introducing electron-deficient bonds (as in boron hydrides). It has accounted for many rearrangements of stable cations. As a "side" result our knowledge has been extended about ionization processes in a solution, as well as about stereochemical methods. 2 Main Terms of Nonclassical Carbocations In 1939 Hevell, Salas and Wilson 23) assumed an intermediate, "bridge" ion 2 to be formed when camphene hydrochloride 1 is rearranged into isobornyl chloride 3. This happened 17 years after Meerwein first postulated the intermediate formation of "carbonium" ions in chemical reactions.

The papers collected in this volume were presented at the International Symposium on Methods and Materials in Microelectronic Technology. This symposium was sponsored by IBM Germany, and it was held September 29 - October 1, 1982, in Bad Neuenahr, West Germany. The progress of semiconductor and microelectronic technology has become so rapid and the field so sophisticated that it is imperative to exchange the latest insight gained as frequently as it can be accomplished. In addition, it is peculiar for this field that the bulk of the investigations are carried out at industrial research and development laboratories, which makes some of the results less readily accessible. Because of these circumstances, the academic community, which among other things, is supposed to communicate the prog ress in this field to students of different disciplines, finds it rather difficult to stay properly informed. It was the intent of this IBM sponsored symposium to bring together key scientists from academic institutions, primarily from Europe, with principal investigators of the industrial scene. Accordingly, this symposium exposed technologists to scientists and vice versa. Scientific advances often lead directly to technological innovations. In turn, new technologies are often arrived at empirically and, because of that, are initially poorly understood. Scientific inquiry then attempts to probe these processes and phenomena in order to achieve a better understanding. Thus science and technology are intricately interconnected, and it is important that technical exchange between technolo gists and scientists is facilitated, since the problems are typically interdiscipli nary in nature."

Over the past decade high performance computing has demonstrated the ability to model and predict accurately a wide range of physical properties and phenomena. Many of these have had an important impact in contributing to wealth creation and improving the quality of life through the development of new products and processes with greater efficacy, efficiency or reduced harmful side effects, and in contributing to our ability to understand and describe the world around us. Following a survey ofthe U.K.'s urgent need for a supercomputingfacility for aca demic research (see next chapter), a 256-processor T3D system from Cray Research Inc. went into operation at the University of Edinburgh in the summer of 1994. The High Performance Computing Initiative, HPCI, was established in November 1994 to support and ensure the efficient and effective exploitation of the T3D (and future gen erations of HPC systems) by a number of consortia working in the "frontier" areas of computational research. The Cray T3D, now comprising 512 processors and total of 32 CB memory, represented a very significant increase in computing power, allowing simulations to move forward on a number offronts. The three-fold aims of the HPCI may be summarised as follows; (1) to seek and maintain a world class position incomputational scienceand engineering, (2) to support and promote exploitation of HPC in industry, commerce and business, and (3) to support education and training in HPC and its application.

A summary of all the most important aspects of supramolecular science, from molecular recognition in chemical and biological systems to supramolecular devices, materials and catalysis. The 17 chapters cover calixarenes, catenanes, cavitands, cholophanes, dendrimers, membranes and self-assembly systems, molecular modelling, molecular level devices, organic materials, peptides and protein surfaces, recognition of carbohydrates, rotaxanes, supramolecular catalysis. A forward-looking chapter written by J.-M. Lehn indicated the future prospects for the entire field. Audience: Ph.D. students and young researchers in chemistry, physics and biology.

From the beginnings of modern chemistry, molecular structure has been a lively area of research and speculation. For more than half a century spectroscopy and other methods have been available to characterize the structures and shapes of molecules, particularly those that are rigid. However, most molecules are at least to some degree non-rigid and this non-rigidity plays an important role in such diverse areas as biological activity, energy transfer, and chemical reactivity. In addition, the large-amplitude vibrations present in non-rigid molecules give rise to unusual low-energy vibrational level patterns which have a dramatic effect on the thermodynamic properties of these systems. Only in recent years has a coherent picture of the energetics and dynamics of the conformational changes inherent in non-rigid (and semi-rigid) molecules begun to emerge. Advances have been made in a number of different experimental areas: vibrational (infrared and Raman) spectroscopy, rotational (microwave) spectroscopy, electron diffraction, and, most recently, laser techniques probing both the ground and excited electronic states. Theoretically, the proliferation of powerful computers coupled with scientific insight has allowed both empirical and ab initio methods to increase our understanding of the forces responsible for the structures and energies of non-rigid systems. The development of theory (group theoretical methods and potential energy surfaces) to understand the unique characteristics of the spectra of these floppy molecules has also been necessary to reach our present level of understanding. The thirty chapters in this volume contributed by the key speakers at the Workshop are divided over the various areas. Both vibrational and rotational spectroscopy have been effective at determining the potential energy surfaces for non-rigid molecules, often in a complementary manner. Recent laser fluorescence work has extended these types of studies to electronic excited states. Electronic diffraction methods provide radial distribution functions from which both molecular structures and compositions of conformational mixtures can be found. Ab initio calculations have progressed substantially over the past few years, and, when carried out at a sufficiently high level, can accurately reproduce (or predict ahead of time) experimental findings. Much of the controversy of the ARW related to the question of when an ab initio is reliable. Since the computer programs are readily available, many poor calculations have been carried out. However, excellent results can be obtained from computations when properly done. A similar situation exists for experimental analyses. The complexities of non-rigid molecules are many, but major strides have been taken to understand their structures and conformational processes.

The ideas of probability are all around us. Lotteries, casino gambling, the al most non-stop polling which seems to mold public policy more and more these are a few of the areas where principles of probability impinge in a direct way on the lives and fortunes of the general public. At a more re moved level there is modern science which uses probability and its offshoots like statistics and the theory of random processes to build mathematical descriptions of the real world. In fact, twentieth-century physics, in embrac ing quantum mechanics, has a world view that is at its core probabilistic in nature, contrary to the deterministic one of classical physics. In addition to all this muscular evidence of the importance of probability ideas it should also be said that probability can be lots of fun. It is a subject where you can start thinking about amusing, interesting, and often difficult problems with very little mathematical background. In this book, I wanted to introduce a reader with at least a fairly decent mathematical background in elementary algebra to this world of probabil ity, to the way of thinking typical of probability, and the kinds of problems to which probability can be applied. I have used examples from a wide variety of fields to motivate the discussion of concepts."

"Kinetics and Dynamics" on molecular modeling of dynamic processes opens with an introductory overview before discussing approaches to reactivity of small systems in the gas phase. Then it examines studies of systems of increasing complexity up to the dynamics of DNA. This title has interdisciplinary character presenting wherever possible an interplay between the theory and the experiment. It provides basic information as well as the details of theory and examples of its application to experimentalists and theoreticians interested in modeling of dynamic processes in chemical and biochemical systems. All contributing authors are renowned experts in their fields and topics covered in this volume represent the forefront of today's science.

Both molecular spectroscopy and computational chemistry have witnessed rapid significant progresses in recent years. On the one hand, it is nowadays possible to compute, to quite a reasonable degree of accuracy, almost all fundamental spectroscopic properties for small molecular systems. The theoretical approach is now properly considered to be of fundamental importance in attaining a high degree of understanding of spectroscopic information. Moreover, it may be also a great help in designing and planning experiments. On the other hand, new and very powerful experimental techniques have been developed. This book combines an advanced teaching standpoint with an emphasis on the interplay between theoretical and experimental molecular spectroscopy. It covers a wide range of topics (such as molecular dynamics and reactivity, conformational analysis, hydrogen bonding and solvent effects, spectroscopy of excited states, complex spectra interpretation and simulation, software development and biochemical applications of molecular spectroscopy) and considers a large variety of molecular spectroscopic techniques, either from an experimental or from a theoretical perspective. (short text) This book combines an advanced teaching standpoint with an emphasis on the interplay between theoretical and experimental molecular spectroscopy. It covers a wide range of topics (such as molecular dynamics and reactivity, conformational analysis, hydrogen bonding and solvent effects, spectroscopy of excited states, complex spectra interpretation and simulation, software development and biochemical applications of molecular spectroscopy) and considers a large variety of molecular spectroscopic techniques either from an experimental or from a theoretical perspective.

Density Functional Theory (DFT) has firmly established itself as the workhorse for atomic-level simulations of condensed phases, pure or composite materials and quantum chemical systems. This work offers a rigorous and detailed introduction to the foundations of this theory, up to and including such advanced topics as orbital-dependent functionals as well as both time-dependent and relativistic DFT. Given the many ramifications of contemporary DFT, the text concentrates on the self-contained presentation of the basics of the most widely used DFT variants: this implies a thorough discussion of the corresponding existence theorems and effective single particle equations, as well as of key approximations utilized in implementations. The formal results are complemented by selected quantitative results, which primarily aim at illustrating the strengths and weaknesses of particular approaches or functionals. The structure and content of this book allow a tutorial and modular self-study approach: the reader will find that all concepts of many-body theory which are indispensable for the discussion of DFT - such as the single-particle Green's function or response functions - are introduced step by step, along with the actual DFT material. The same applies to basic notions of solid state theory, such as the Fermi surface of inhomogeneous, interacting systems. In fact, even the language of second quantization is introduced systematically in an Appendix for readers without formal training in many-body theory.