This monograph develops a new way of justifying the claims made by science about phenomenon not directly observable by humans, such as atoms and black holes. It details a way of making inferences to the existence and properties of unobservable entities and states of affairs that can be given a probabilistic justification. The inferences used to establish realist claims are not a form of, and neither do they rely on, inference to the best explanation. Scientific Realism maintains that scientific theories and hypotheses refer to real entities, forces, and relations, even if one cannot examine them. But, there are those who doubt these claims. The author develops a novel way of defending Scientific Realism against a range of influential attacks. He argues that in some cases, at least, we can make probabilistically justifiable inferences from observed data to claims about unobservable, theoretical entities. He shows how this enables us to place some scientific realist claims on a firmer epistemological footing than has previously been the case. This also makes it possible to give a unified set of replies to the most common objections to Scientific Realism. The final chapters apply the developed conceptual apparatus to key cases from the history of science and from recent science. One example concerns realism with respect to atoms. Another looks at inferences from recent astronomical data to conclusions about the size and shape of those parts of the universe lying beyond that which we can observe.

This thesis presents detailed mechanistic studies on a series of important C-H activation reactions using combined computational methods and mass spectrometry experiments. It also provides guidance on the design and improvement of catalysts and ligands. The reactions investigated include: (i) a nitrile-containing template-assisted meta-selective C-H activation, (ii) Pd/mono-N-protected amino acid (MPAA) catalyzed meta-selective C-H activation, (iii) Pd/MPAA catalyzed asymmetric C-H activation reactions, and (iv) Cu-catalyzed sp3 C-H cross-dehydrogenative-coupling reaction. The book reports on a novel dimeric Pd-M (M = Pd or Ag) model for reaction (i), which successfully explains the meta-selectivity observed experimentally. For reaction (ii), with a combined DFT/MS method, the author successfully reveals the roles of MPAA ligands and a new C-H activation mechanism, which accounts for the improved reactivity and high meta-selectivity and opens new avenues for ligand design. She subsequently applies ion-mobility mass spectrometry to capture and separate the [Pd(MPAA)(substrate)] complex at different stages for the first time, providing support for the internal-base model for reaction (iii). Employing DFT studies, she then establishes a chirality relay model that can be widely applied to MPAA-assisted asymmetric C-H activation reactions. Lastly, for reaction (iv) the author conducts detailed computational studies on several plausible pathways for Cu/O2 and Cu/TBHP systems and finds a reliable method for calculating the single electron transfer (SET) process on the basis of benchmark studies.

The development and computational implementation of analytical expres sions for the low-order derivatives of electronic energy surfaces and other molecular properties has undergone rapid growth in recent years. It is now fairly routine for chemists to make use of energy gradient information in locating and identifying stable geometries and transition states. The use of second analytical derivative (Hessian or curvature) expressions is not yet routine, and third and higher energy derivatives as well as property (e.g., dipole moment, polarizability) derivatives are just beginning to be applied to chemical problems. This NATO Advanced Research Workshop focused on analyzing the re lative merits of various strategies for deriving the requisite analyti cal expressions, for computing necessary integral derivatives and wave function parameter derivatives, and for efficiently coding these expres sions on conventional scalar machines and vector-oriented computers. The participant list contained many scientists who have been instrumen tal in bringing this field to fruition as well as eminent scientists who have broad knowledge and experience in quantum chemistry in general."

Science advances by leaps and bounds rather than linearly in time. I t is not uncommon for a new concept or approach to generate a lot of initial interest, only to enter a quiet period of years or decades and then suddenly reemerge as the focus of new exciting investigations. This is certainly the case of the reduced density matrices (a k a N-matrices or RDMs), whose promise of a great simplification of quantum-chemical approaches faded away when the prospects of formulating the auxil iary yet essential N-representability conditions turned quite bleak. How ever, even during the period that followed this initial disappointment, the 2-matrices and their one-particle counterparts have been ubiquitous in the formalisms of modern electronic structure theory, entering the correlated-level expressions for the first-order response properties, giv ing rise to natural spinorbitals employed in the configuration interaction method and in rigorous analysis of electronic wavefunctions, and al lowing direct calculations of ionization potentials through the extended Koopmans'theorem. The recent research of Nakatsuji, Valdemoro, and Mazziotti her alds a renaissance of the concept of RDlvls that promotes them from the role of interpretive tools and auxiliary quantities to that of central variables of new electron correlation formalisms. Thanks to the economy of information offered by RDMs, these formalisms surpass the conven tional approaches in conciseness and elegance of formulation. As such, they hold the promise of opening an entirely new chapter of quantum chemistry."

Providing the quantum-mechanical foundations of chemical bonding, this unique textbook emphasizes key concepts such as superposition, degeneracy of states and the role of the electron spin. An initial, concise and compact presentation of the rudiments of quantum mechanics enables readers to progress through the book with a firm grounding. Experimental examples are included to illustrate how the abstract concepts are manifest in real systems.

Quantum mechanical calculations in physics, chemistry and biology are widely recognized as useful interpretative and predictive tools. Unfortunately, they are plagued by unfavorable convergence limitations due to the use of finite linear combinations of basis functions. With the current computer technologies, there is a possible way out to the situation by solving numerically the corresponding wave equations. The present interest and need for numerical determination of electronic structure of atoms, diatomic and poly atomic molecules led us to organize a NATO-ARW devoted to these questions. The aim of the meeting was to provide a review of the state of the art about techniques and applications. The organizing committee consisted of Drs. G. Berthier, P. Claverie, M. Defranceschi, J. Delhalle, H.J. Monkhorst and P. Pyykk6. It was a great sorrow for us to be informed in January 88 of the death of Professor P. Claverie who supported so enthusiastically the idea of having such a meeting organized. The NATO Advanced Research Worshop on : " Numerical Determination of the Electronic Structure of Atoms, Diatomic and Poly atomic Molecules" was held at Versailles (France) from April 17th till April 22th, 1988.

This book contains the transcripts of the lectures presented at the NATO Advanced study Institute on "Computational Techniques in Quantum Chemistry and Molecular Physics," held at Ramsau, Germany, 4th - 21st Sept. 1974. Quantum theory was developed in the early decades of this century and was first applied to problems in chemistry and molecular physics as early as 1927. It soon emerged however, that it was impossible to con sider any but the simplest systems in any quantita tive detail because of the complexity of Schrodinger's equation which is the basic equation for chemical and molecular physics applications. This remained the si tuation until the development, after 1950, of elec tronic digital computers. It then became possible to attempt approximate solutions of Schrodinger's equa tion for fairly complicated systems, to yield results which were sufficiently accurate to make comparison with experiment meaningful. Starting in the early nineteen sixties in the United States at a few centres with access to good computers an enormous amount of work went into the development and implementation of schemes for approximate solu tions of Schrodinger's equation, particularly the de velopment of the Hartree-Fock self-consistent-field scheme. But it was soon found that the integrals needed for application of the methods to molecular problems are far from trivial to evaluate and cannot be easily approximated."

Advances in Quantum Methods and Applications in Chemistry, Physics, and Biology includes peer-reviewed contributions based on carefully selected presentations given at the 17th International Workshop on Quantum Systems in Chemistry, Physics, and Biology. New trends and state-of-the-art developments in the quantum theory of atomic and molecular systems, and condensed matter (including biological systems and nanostructures) are described by academics of international distinction.

Development in science depends on several factors. Among these, the role of individual scientists is perhaps not the most important one. Science is typically a body of collective knowledge and any increase in the amount of this knowledge is certainly due to strong interaction among scientists. Even in the past, it happened quite rarely that a single person, without any aid of others, d- covered something fundamental or opened a new chapter in science. Great figures of science history have, in most cases, had rather a summarizing and s- thesizing role. This is especially valid over the last few decades. On one hand, the amount of information necessary to achieve new discoveries, has increased tremendously. On the other hand, improvement of technical facilities has increased the speed of information exchange. These factors resulted in a degree of specialization in science that had never seen before. Most of us are experts and specialists rather than scientists in the classical sense. My personal feeling is that, even nowadays, there is a strong need for professionals with a broad knowledge and c- prehensive mind, although they may not be competitive in the number of their publications or the sizes of their grants. Every time I have met such a person (I can count these cases on my fingers) I have become deeply influenced by his or her strong intellect.

"Astrochemistry and Astrobiology" is the debut volume in the new series "Physical Chemistry in Action." Aimed at both the novice and experienced researcher, this volume outlines the physico-chemical principles which underpin our attempts to understand astrochemistry and predict astrobiology. An introductory chapter includes fundamental aspects of physical chemistry required for understanding the field. Eight further chapters address specific topics, encompassing basic theory and models, up-to-date research and an outlook on future work. The last chapter examines each of the topics again but addressed from a different angle. Written and edited by international experts, this text is accessible for those entering the field of astrochemistry and astrobiology, while it still remains interesting for more experienced researchers.

"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."

The interactions of DNA with force are central to manifold fields of inquiry, including the de novo design of DNA nanostructures, the use of DNA to probe the principles of biological self-assembly, and the operation of cellular nanomachines. This work presents a survey of three distinct ways coarse-grained simulations can help characterize these interactions. A non-equilibrium energy landscape reconstruction technique is validated for use with the oxDNA model and a practical framework to guide future applications is established. A novel method for calculating entropic forces in DNA molecules is outlined and contrasted with existing, flawed approaches. Finally, a joint experimental-simulation study of large DNA origami nanostructures under force sheds light on design principles and, through vivid illustrations, their unfolding process. This text provides an accessible and exciting launching point for any student interested in the computational study of DNA mechanics and force interactions.

This book focuses on the electronic properties of transition metals in coordination environments. These properties are responsible for the unique and intricate activity of transition metal sites in bio- and inorganic catalysis, but also pose challenges for both theoretical and experimental studies. Written by an international group of recognized experts, the book reviews recent advances in computational modeling and discusses their interplay using experiments. It covers a broad range of topics, including advanced computational methods for transition metal systems; spectroscopic, electrochemical and catalytic properties of transition metals in coordination environments; metalloenzymes and biomimetic compounds; and spin-related phenomena. As such, the book offers an invaluable resource for all researchers and postgraduate students interested in both fundamental and application-oriented research in the field of transition metal systems.

Chemical structure and bonding. The scope of the series spans the entire Periodic Table and addresses structure and bonding issues associated with all of the elements. It also focuses attention on new and developing areas of modern structural and theoretical chemistry such as nanostructures, molecular electronics, designed molecular solids, surfaces, metal clusters and supramolecular structures. Physical and spectroscopic techniques used to determine, examine and model structures fall within the purview of Structure and Bonding to the extent that the focus is on the scientific results obtained and not on specialist information concerning the techniques themselves. Issues associated with the development of bonding models and generalizations that illuminate the reactivity pathways and rates of chemical processes are also relevant. The individual volumes in the series are thematic. The goal of each volume is to give the reader, whether at a university or in industry, a comprehensive overview of an area where new insights are emerging that are of interest to a larger scientific audience.

This open access book brings out the state of the art on how informatics-based tools are used and expected to be used in nanomaterials research. There has been great progress in the area in which "big-data" generated by experiments or computations are fully utilized to accelerate discovery of new materials, key factors, and design rules. Data-intensive approaches play indispensable roles in advanced materials characterization. "Materials informatics" is the central paradigm in the new trend. "Nanoinformatics" is its essential subset, which focuses on nanostructures of materials such as surfaces, interfaces, dopants, and point defects, playing a critical role in determining materials properties. There have been significant advances in experimental and computational techniques to characterize individual atoms in nanostructures and to gain quantitative information. The collaboration of researchers in materials science and information science is growing actively and is creating a new trend in materials science and engineering.

The fourth edition of "Quantum Chemistry" is an updated textbook on the subject covering the model syllabi of various undergraduate and postgraduate courses. The book contains the basics of quantum mechanics and quantum mechanical laws; applications of translational, vibrational and rotational motions of sub-atomic particles; theories of harmonic oscillator and atomic structure etc. The Hartree Fock self-consistent field methods, configuration, interaction, extended Huckel theory etc. are all presented with utmost clarity and examples. The present edition contains a chapter on matrix-vector methods of quantum mechanics as well as one on density functional theory along with molecular symmetry and group theory with applications to molecular orbital treatment. Steps involved in mathematical derivations are presented in full, leaving no ambiguity. Illustrative examples and practice problems, with hints are provided in each chapter.

th The 13 Jerusalem Symposium on Quantum Chemistry and Bio- chemistry was dedicated to the memory of Ernst David Bergmann, one of the founders of this series of Symposia, at the occasion of the 5th anniversary of his death. The opening session was honored by the pre- sence of H. E. Yzhak Navon, President of the State of Israel and of Baron Edmond de Rothschild whose generous and constant support makes these Symposia possible. To both these distinguished guests we address the expression of our deep gratitude. Our thanks are also due to the Israel Academy of Sciences and Humanities, in particular to its President Professor Aryeh Dvoretzky and to the Hebrew University of Jerusalem for their hospita- lity and helpful association. I had the privilege this time to join efforts in the organi- zation of this Symposium with two distinguished American colleagues, Prof. P. O. P. Ts'o from Johns Hopkins University and Dr. Harry Gelboin from the National Institute for Cancer Research. I wish to thank them for their invaluable help and the two Institutions which they repre- sent for important financial support. th The subject of the 13 Jerusalem Symposium brings us back to that of the 1st Symposium held in 1967. The comparison of the two Proceedings enables us to evaluate the important developments which occurred in this field of research during the last 13 years.

Polyoxometalates (POMs) form a large, distinctive class of molecular inorganic compounds of unrivaled electronic versatility and structural variation, with impacts ranging from chemistry, catalysis, and materials science to biology, and medicine. This book covers the basic principles governing the structure, bonding and reactivity of these metal-oxygen cluster anions and the major developments in their molecular science.

The book comprises three sections. The first covers areas ranging from topological principles via synthesis and stability to reactivity in solution. It also focuses on the physical methods currently used to extract information on the molecular and electronic structures as well as the physical properties of these clusters. The second part reviews different types of POMs, focusing on those systems that currently impact other areas of interest, such as supramolecular chemistry, nanochemistry and molecular magnetism. The third section is devoted to POM-based materials and their applications and prospects in catalysis and materials science.

In this dissertation, Marie-Helene Larraufie develops original radical and pallado-catalyzed methodologies to enable the synthesis of several classes of bioactive nitrogen-containing heterocycles. New radical cascades employing the N-acylcyanamide moiety offer straightforward routes to quinazolinones and guanidines, as well as new insights into the mechanism of homolytic aromatic substitutions. In parallel, Larraufie expands the scope of visible light photoredox catalysis to the ring opening of epoxides and aziridines, thus providing new sustainable alternatives for the generation of radicals. Furthermore, in a collaborative effort with the Catellani group, the author investigates dual palladium/norbornene catalysis. First, she develops a C-amination coupling variant of the Catellani reaction with unprotected amines which provides an expeditious route to phenanthridines. Then, she examines the influence of the chelating effect on Pd(IV) intermediates reactivity with the help of experimental studies and DFT calculations. The work in this thesis has resulted in numerous publications in high impact journals.The clarity and depth of the experimental section will be useful for students and researchers working in this field.

Special numerical techniques are already needed to deal with nxn matrices for large n.Tensor data are of size nxnx...xn=n DEGREESd, where n DEGREESd exceeds the computer memory by far. They appear for problems of high spatial dimensions. Since standard methods fail, a particular tensor calculus is needed to treat such problems. The monograph describes the methods how tensors can be practically treated and how numerical operations can be performed. Applications are problems from quantum chemistry, approximation of multivariate functions, solution of pde, e.g., with stochastic coefficie

The third and last volume of this treatise IS concerned with important applications of the quantum~theory of chemical reactions to chemisorption, catalysis and biochemical reactions. The book begins with an important paper devoted to the theoretical background of heterogeneous catalysis. It is followed by two papers showing typical applications of wave mechanics to the analysis of chemisorption. Catalysed gas-solid reactions are chosen to illustrate gas, organic solid state reaction and some aspects of the mechanism of the FISCHER-TROPSCH synthesis are presented. The second part of the book is devoted to biochemical applications of quantum chemistry. Two papers are concerned with the quantum theory of enzyme activity. Two others present recent progress of quantum pharmacology. Finally an important contribution to the theory of intermolecular forces is made in the view of possible applications to biochemical problems. vii R. Daudel, A. Pullman, L. Salem, and A. Viellard reds.), Quantum Theory o/Chemical Reactions, Volume III, vii. Copyright (c) 1982 by D. Reidel Publishing Company. THEORETICAL BACKGROUND OF HETEROGENEOUS CATALYSIS J.E.Germain Laboratoire de Catalyse Appliquee et Cinetique Heterogene L. A. 231 du Centre National de la Recherche Scientifique Universite Claude Bernard Lyon I, E.S.C.I.L. 43 Boulevard du 11 Novembre 1918, 69622 Villeurbanne Cedex. Heterogeneous Catalysis is a surface Kinetic phenomenon by which a chemical reaction between molecules of a fluid phase is accelerated (activity) and oriented (selectivity) by contact with a solid phase (catalysts, without change of the solid.

This book presents a number of studies on the molecular dynamics of cement-based materials. It introduces a practical molecular model of cement-hydrate, delineates the relationship between molecular structure and nanoscale properties, reveals the transport mechanism of cement-hydrate, and provides useful methods for material design. Based on the molecular model presented here, the book subsequently sheds light on nanotechnology applications in the design of construction and building materials. As such, it offers a valuable asset for researchers, scientists, and engineers in the field of construction and building materials.

The technique of smal1-angle soattering (SAS) is now about sixty years o1d. Soon after the first observations of, a continuous, intense X-ray scattering near the primary beam from samp1es such as canbo:tt,bla:cks, it was recognized that this scattering arose from e1ectron density heterogeneities on a scale of severa! tens to severa! hundred times the wave1ength of the radiation used. By the time the classic monograph of Guinier and Foumet appeared in 1955, much of the basic theory and instrumentation had been developed, and applications to colloidal suspensions, macromolecular solutions inc1uding proteins and viruses, fibers, porous and finely divided solids, metallic alloys etc. numbered in the hundreds. Following severa! specialized meetings, the first international conference on small-ang1e X-ray scattering was helditi, Syracuse in 1965, marked by the presentation of new scattering theory for polydisperse systems, polymer coils and filaments, new instrumentation (the Bonse-Hart camera), and new applications to polymeric, biologica!, and metallic systems, to critica! phenomena and to catalysts. The second conference (Graz, 1970) no longer dealt exclusively with X- ray scattering, but also inc1uded neutron small-angle scattering (SANS). SANS applications developed rapidly during this period, especially for studying synthetic and biologica! macromolecules, when the possibilities of exploiting scattering Iength density differences, created by selective deuteration, were recognized.

In this thesis, the author introduces two strategies used to construct various types of N-heterocycles, based on the chemistry of zirconacycles and 2,6-diazasemibullvalenes. In the first part, the author presents the development of multi-component cyclization of a zirconacyclobutene-silacyclobutene fused compound, nitriles and unsaturated compounds. These reactions provide synthetically useful methodology for various N-heterocycles such as 3-acyl pyrrole, pyrrolo[3,2-d]pyridazine and dihydropyrroloazepine, which are all difficult to synthesize by other means. The isolation and characterization of the key three-fused-ring Zr/Si-containing intermediates are also described in detail. These results show that the zirconacyclobutene-silacyclobutene fused compound behaves as a "chemical transformer" upon treatment with various substrates via the "coordination-induced skeleton rearrangement" mechanism. In the second part, the author demonstrates the synthesis and isolation of a series of 2,6-diazasemibullvalenes (NSBVs) from the reaction of 1,4-dilithio-1,3-dienes and nitriles, highlighting the significant progress made for the first time in this work: (1) determination of X-ray crystal structure of a substituted 2,6-diazasemibullvalene; (2) measurement of the activation barrier of its rapid intramolecular aza-Cope rearrangement in solution; (3) exploration of several reaction types of NSBV with diverse ring-expansion products and "bowl-shape" or "cage-shape" N-containing polycyclic skeletons; (4) demonstration of the localized structure as the predominant form and the homoaromatic delocalized structure as a minor component in the equilibrium using theoretical analysis. Based on well-founded results, this work sheds new light on this controversial topic.

This volume is a description of the current knowledge on the different metal-oxo and metal-peroxo species involved in catalytic oxidations. The series contains critical reviews of the present position and future trends, and short and concise reports written by the world's renowned experts.