# Book Review Ab Initio Methods in Quantum Chemistry Part I and Part II (Series Advances in Chemical Physics Vols. 67 and 69). Series editors I. Prigogine and S. A. Rice; volume editor K. P

код для вставкиСкачатьBOOK R E V I E W S A6 Initio Methods in Quantum Chemistry, Part I and Part I1 (Series: Advances in Chemical Physics, Vols. 67 and 69). Series editors: I . Prigogine and S . A . Rice; volume editor: K . P. Lawley. Wiley, Chichester 1987. Part I: 556 pp., bound, E 65.00.--ISBN 0-471-90900-9; Part 11: 588 pp., bound, E 59.95.--ISBN 0-471-90901-7 To the series “Advances in Chemical Physics”, well known for its high quality, two extensive new volumes devoted to ab initio quantum chemistry have now been added, increasing the number of volumes in the series to 69. The aim of the editors of this series is to bring together in a single work review articles o n specialist topics by internationally known experts, so as make new ideas in chemical physics accessible to a wide readership. The authors are encouraged to bring to task their own individual evaluations and viewpoints. Here once more those aims have been fulfilled very successfully. The books contain a wealth of new and highly interesting information and ideas, not only for theoreticians but also for experimentalists who need theory to help in guiding their work. The first contribution in Part I (by Bruna and Peyerimhoff) is on electronic excited states, and comes from the Bonn group which is very active in this field; it contains a detailed survey of calculated properties, mainly of diatomic and triatomic molecules. It is clearly presented, and the schematic layout contributes to rapid assimilation of the ideas. This article will be greatly welcomed not only by quantum chemists but also by all who have a n interest in the spectroscopic properties of small molecules. The article by Amos deals with the calculation of functions describing molecular properties, with special emphasis on methods for directly calculating dipolar properties and polarizabilities. The power of the theory is illustrated by numerous examples of calculations of IR and Raman intensities. In another contribution Bernardi and Robb have undertaken the important task of giving a critical summary of theoretical knowledge on mechanisms of typical reactions, mainly organic. Such studies would not be possible without using numerical methods to locate the extrema o n multidimensional potential energy surfaces. The algorithms used for this purpose are described in a clear and comprehensible fashion in the article by Schlegel. Balasubramanian and Pitzer give details of the methods now available for calculations of relativistic effects, and describe various applications of relativistic quantum chemistry, mainly to spectroscopic problems. Durand and Malrieu have undertaken a detailed study of effective Hamiltonian operators and their physical significance. Jones describes methods and results based o n the formalism of density functions. Wilson deals with the question of choosing between different basis sets and applying them. Lastly, Ahlrichs and Scharfgive a concise description of methods based o n coupled pairs approximations. In this important and interesting contribution, the various methods are critically compared and their advantages and disadvantages are discussed with the help of examples. It seems impossible now to escape the increasing flood of new abbreviations to describe ever more detailed aspects of solutions of the Schrodinger equation for the motions of electrons and nuclei. Not only will most scientists working in the field be unaware, for example, that CEPA is also a botanical abbreviation defining the edible onion Angew. Chem. lilt Ed. Engl. 27 (1988) No. 7 family, they are also likely to have difficulty with creations which they are often assumed to be familiar with such as WNR (wavefunction Hessian matrix Newton-Raphson), APT (atomic polar tensors), or SAC (symmetry adapted cluster approach). In view of the large number of new abbreviations, it would have been sensible to include in both volumes a glossary of these terms with explanations, and perhaps also literature references. In contrast, the index of cited authors contained in the book does not seem particularly useful, as each article has its own separate bibliography. In my opinion neither book is really suitable as an introduction to ab initio methods in quantum chemistry, which was the declared intention of the editors. Taken as a whole, the first volume can be recommended to all readers who have some knowledge of or interest in ab initio methods in quantum chemistry. They will find much new material here, and in addition to its other merits the book is an extremely useful up-to-date work of reference on specialized aspects of theoretical chemistry. These are qualities which the “Advances in Chemical Physics” series has now been providing in an outstanding way for nearly thirty years, covering many fields of research. The second volume is mainly concerned with modern algorithms of quantum chemistry. Five of the nine contributions deal with multi-configurational methods and their applications. Advanced ab initio methods of this kind are indispensable in, for example, exact calculations of dissociation energies, for calculations on near-degenerate electronic states, for dealing with regions in which a crossover of potentials is just avoided, and for spin coupling effects. The last few years have seen the introduction of new numerical methods, largely based on group theory considerations, which allow efficient handling of multi-reference problems. The application of these methods has been greatly helped by progress in computer technology, with the advent of large capacity vector-processing computers and super-minicomputers. These methods make it possible to solve problems formulated in more and more general terms. The appearance of this book is very much to be welcomed, since it deals with the latest developments and will undoubtedly have a stimulating effect. The book begins with an article by Werner on direct methods for the solution of multi-reference problems involving configurational interaction. The author begins by describing his recent work on MCSCF methods which give fast and certain convergence, and on direct methods for the solution of the MCSCF-CI problem. All the algorithms described are especially suitable for vector computers. The article is very well written from a teaching standpoint, contains many new ideas, and can be warmly recommended to all who are interested in modern MCSCF methods. Shepard, in a very detailed contribution (134 pages!), reviews the development of MCSCF methods and discusses the different ways in which they can be formulated. Roos deals with the special case of the MCSCF method in which one considers all configurations for a given number of molecular orbitals. Valence bond methods, although they are based on a different theoretical model, are used for the same purposes as MCSCF methods. The present state of knowledge on these methods is reviewed by Cooper, Geratt, and Raimondi. The theoretical treatment of transition metal compounds usually requires multi-reference methods. Salahub gives a n excellent overview of methods ap983 plied to transition metal atoms and their dimers. This contribution can be recommended as a source of information for readers interested in the theory of chemical bonding involving metals. The calculation of potential energy surfaces for weakly bonded systems continues to present a great challenge for ab initio quantum chemical methods, as discussed in the contribution by van Lenthe, van Diujneveldt, and van de Rijdt, with particular attention to the basis superposition effect. A very competent article on analytical derivation methods in quantum chemistry is provided by Pulay, one of the pioneers in this highly topical area of research. As well as reviewing these methods, the author gives a critical appraisal and indicates possibilities for further developments. This contribution too is very valuable from a teaching standpoint. Oddershede deals with the propagator methods, which are especially useful for electronic excited states and applications such as calculation of dynamic polarizabilities. Everyone interested in previous work based on this formalism will find here a useful review and commentary on the methods. Finally, Dunlop discusses symmetry and degeneracy in the theory of Xcr functions and density functions. This second volume, containing articles which are more oriented towards methodology, is aimed at the specialist to an even greater extent than is the first volume. The individual articles are of excellent quality, and they deal with topical research themes which are still rapidly developing. Consequently, the book will not only be indispensable for libraries, but will also provide theoreticians with a starting point for further developments in their armory of techniques. Pave1 Rosmus [NB 859 IE] Institut fur Anorganische Chemie der Universitat Frankfurt/Main (FRG) Principles and Applications of Organotransition Metal Chemistry. By J . P. Collman, L. G . Hegedus. J . R . Norton, and R . G. Finke. Oxford University Press, Oxford 1987. xii, 989 pp., bound, S 40.00.--ISBN 0-93570251-2 When the first edition of Coliman and Hegedus appeared on the market seven years ago it did not seem very impressive. It was made by direct reproduction of a typescript, with a result which was not altogether attractive to the eye, and it also contained many errors, especially in structural formulas and equations. However, even then a closer study of the book revealed its merits: for the first time it attempted, in a skilful and instructive way, to bridge the gulf between fundamental knowledge of organotransition metal chemistry and its importance for catalytic process technology, and also to show how this knowledge could be applied in organic synthesis. The success of the textbook was therefore already assured, despite the unsatisfactory manner of its production. The second edition is now available; it has, naturally, turned out to be somewhat larger, and the involvement as co-authors of a further two organometallic chemists, J . R. Norton and R . G. Finke, who have a more inorganic bias, has remedied some weak points of the first edition. The text is divided into three parts: I. Basic Principles, 11. Catalytic Processes and 111. Applications to Organic Synthesis; their respective lengths of 500,140 and 270 pages seem appropriate to the subject matter. The longest, Part I, begins by discussing structure and bonding, then continues with a survey of the various types 984 of organotransition metal complexes, arranged according to the nature of the ligands. This is followed by a very thorough treatment of the most important types of reactions which the previously listed complexes are known to undergo, discussed under the headings of ligand exchange processes, oxidative additions and reductive eliminations, intramolecular insertion reactions, and lastly nucleophilic and electrophilic attack of ligands. The majority of the examples are well chosen, and the sections on individual topics include details even of very recent and highly topical results, e.g. on electron transfer catalysis in substitution reactions, the oxidative addition of Si-H and C-H bonds to transition metals, carbene insertions, MHC three-centre bonding, and complexes containing SO, SOz, COz, NS o r diazoalkanes as ligands. Part I is concluded by a chapter on metallacycles, including discussions of olefin metathesis and other important reactions which involve metallacyclobutanes. In Part I1 the discussion of catalytic processes begins with homogeneous catalytic hydrogenation, hydrosilylation and hydrocyanation, then continues with the metalcatalyzed polymerizations of olefins and acetylenes, and concludes with a concise survey of catalytic reactions involving carbon monoxide. In this chapter the Roelen 0x0 synthesis (hydroformylation), the Monsanto acetic acid process, and, of course, the Fischer-Tropsch synthesis are discussed. Commendable features of the treatment are that modern variations of well-known processes are also described in detail (e.g. the manufacture of ethylene glycol by the Fischer-Tropsch process), and that up-to-date figures relating to industrial production are given. Part 111, covering applications in organic synthesis, has without doubt undergone the greatest changes since the first edition, thereby reflecting one of the most important current trends affecting organometallic chemistry in recent years. Several monographs on the theme of organometallic compounds for organic synthesis have recently appeared in rapid succession, and it is also no accident that since 1981 a series of conferences on this topic has been set up. Here the authors have arranged the material according to the types of organometaliic compounds used, i.e. metal hydride complexes, compounds with M-C o-bonds, carbonyl and carbene complexes, metallacycles, olefin, diolefin, and dienyl compounds, alkyne and ally1 complexes, and finally sandwich complexes formed by arene ligands. One can fairly confidently predict that in the next edition of the book Part 111 will again grow in size. What are the good and bad features of “Collman, Hegedus, Norton and Finke”? The overall concept of the book is undoubtedly good, as is the balance between the different types of compounds and reactions, the way in which the chemistry is related to applications, and the topicality of content. The presentation, the reproduction of structural formulas and the typography are better than in the first edition. Regrettably many printing errors have again crept in (despite proof-reading by four authors). These appear as early as the first page of the contents list (“Formal-Metal Bonds” instead of Formal Metal-Metal Bonds, “Isolabal” instead of Isolobal), and continues through the tables (Historical Landmarks: “Reppe describes the catalytic cyclotrimerization of acetylene to cyclooctatetraene”) to the individual chapters. Especially displeasing are incorrect formulas, as uninitiated readers at least will be confused by these; examples: p. 78, bottom left: this should read five-coordinate osmium(0)-complex, p. 106 bottom left: positive charge missing, p. 153: PtCI,(COD)-not PtC12(COD)2, p. 160: Ru-PPh3-not Ru-PPh,, p. 171: 154 Angew. Chem. Int. Ed. Engl. 27 (1988) No. 7

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