close

Вход

Забыли?

вход по аккаунту

?

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 вставкиСкачать
BOOK 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
Документ
Категория
Без категории
Просмотров
0
Размер файла
297 Кб
Теги
series, physics, method, editor, initio, vols, chemistry, volume, part, advanced, chemical, book, quantum, rice, review, prigogine
1/--страниц
Пожаловаться на содержимое документа