J. CHEM. SOC. FARADAY TRANS., 1994, 90(21), 3373-3375 Techniques and Mechanisms in Electrochemistry. By P. A. Christensen and A. Hamnett. Blackie, Glasgow, 1994.Pp. x + 379.Price f24.94.ISBN 0-7514-0129-3 There has been a flurry of textbooks on electrochemistry in the last two or three years, all emphasizing electrode pro- cesses, but none so clearly focussed on modern developments as this one. The approach is novel and well planned. There are three chapters : 1. Introduction to modern electrochem- istry ; 2. Techniques giving mechanistic information; and 3. Examples of the application of electrochemical methods. Chapter 1 provides a quick scamper through interfacial structure and electrode kinetics in 35 pages. It seems to me doubtful whether an advanced undergraduate would be able to follow this without preparation from a more explanatory text, especially as there are some unhelpful misprints, for example, in the section on reactions with adsorbed inter- mediates (pp.29-33). Chapter 2 is centrally placed and is clearly central to the philosophy of the book. It is a very clearly written intro- duction to many of the techniques now being used by electro- chemists. There are several specialist review series which cover this material, but this will provide a valuable intro- duction to them. It is a little surprising to find the chapter starting with the capillary electrometer which is probably the oldest electochemical apparatus still in use. Also, the descrip- tion of the study of solid surfaces by the piezoelectric method may prove to yield important results, but so far the direct measurement of capacity, which is scarcely mentioned, has provided much more detailed and quantitative information.The first half of the chapter continues with important in situ probes which are surface specific :voltammetry, scanning tun- nelling miroscopy and spectroscopy, atomic force micros- copy, IR and Raman spectroscopies, ellipsometry, X-ray methods and impedance. The second half of Chapter 2 deals with in situ probes of the near-electrode region, and begins with the classical elec- trochemical techniques involving consideration of diffusion, followed by rotating disc and ring, EPR, UV-VIS spectro-scopies, the quartz microbalance, FTIR and electrochemical mass spectrometry.There is a final, short section on ex situ techniques dealing with emersion into UHV and mass spec- trometry. This chapter as a whole is an outstanding summary of the ways in which a modern electrochemist can select techniques which will help to solve a particular problem. The principle of each method is simply and lucidly explained. There is clear information about the practice of each method and its strengths and weaknesses as well as real examples of its use. Chapter 3 provides a number of case histories. The first two, and to some extent the third, are concerned with Pt elec- trodes. The literature on such electrodes is now so enormous that a comprehensive discussion of H and 0 adsorption and methanol oxidation could easily fill a volume this size, espe- cially if one starts from Bowden’s work in 1928, as here.The selection made is reasonable with its emphasis on voltam- metry, ellipsometry and IR studies of polycrystalline Pt. Although some elegant work on single crystal surfaces is mentioned, full advantage of the work of the previous decade is not taken, for example, in explaining the nature of strongly and weakly bound H on the polycrystalline electrodes. This is surprising when the book starts with a fairly detailed account of surface structure. The third section on CO, reduction is similarly detailed, but the complexities of the passive film on Fe are described rather briefly in the 4th section; will a student know about mixed potentials and the significance of Fig.3.66(b)? The penultimate section on polymer (largely poly-pyrrole) films shows a skillful selection of the vast material now accumulated and the final section on enzymes in films points to the furture, some of which is already with us. No book is perfect; there are some things I would have liked to have changed: the perpetuation of the unhelpful n, introduced by Nicholson and Shain (p. 174), the statement that adsorbed H is always in equilibrium with H, (p. 233), the use of diagrams taken from published work without rational- ising the plotting of the potential scale. But despite these, and some other trivial criticisms, I have no hesitation in recom- mending this well produced book with enthusiasm.One of its strongest features is the continual use of real experimental data which keeps the reader in contact with the way electro- chemists carry out fundamental research at the present time. R. Parsons Received 22nd March, 1994 Physical Methods of Chemistry, 2nd Edition, Volume 1XA. Investigations of Surfaces and Interfaces. Ed. B. W. Rossiter and R. C. Baetzold. John Wiley and Sons Ltd, Chichester, 1993.Pp. xii + 516. €98.00. Before a surface can be fully characterised, several questions need to be answered. These include: How much surface is there, measured by which probe? What is the geometry of that available surface? What is its chemical composition? How do these things affect the energetics of the surface? This volume, which arrives towards the end of a well known series, is one of a pair planned to cover the field.There are difficulties, therefore, in assessing this single volume. It does not pretend to answer all of the above ques- tions, since there is hardly a mention of surface area measure- ment, porosity or everyday materials. That the book covers techniques of study and measurement, with no experimental results on materials, as such, takes a little getting used to. The first chapter covers the determination of surface tension of liquids, and the second the study of adsorption from solution: these two chapters are slightly out of tune with the rest of the book since they are ‘older’ techniques. They are brought up to date well by the discussion of more recent methods of measurement. Most of the volume is about assessment of well defined solid surfaces, with many metallic and semiconductor exam- ples.A good chapter on scanning tunneling microscopy covers the widening range of techniques for the atomic resolution of surfaces across a wide range of materials. The bulk of the book is taken up with techniques to study chem- istry at surfaces. These include surface spectroscopic tech- niques such as EELS and SIMS, the use of molecular beams, and laser-induced thermal desorption. These last two discuss reactions of molecules sorbed on metal surfaces rather than the surfaces themselves. The individual chapters are all well worth reading. The starting level of each of them is sensible, and it is useful to be reminded of the limits of each technique, but to be encour- aged to push some techniques further.Many of the chapters have references up to the late eighties and occasionally the early nineties. This is probably reasonable in view of the orientation of the series towards techniques. The editors’ aim ‘to produce an introduction to the field.. . to give a clear understanding ... of the value, potential and limitations of the respective techniques’ has been pretty well met even though this single volume does not give a rounded picture of even most of the techniques available: final judge- ment must wait the arrival of the second volume. M. C. Ball Received 27th April, 1994 Cluster Ions. Wiley Series in Ion Chemistry and Physics.Ed. Cheuk-Yiu Ng, Tomas Baer and Ivan Powis. John Wiley 8 Sons Ltd, Chichester, 1993.Pp. xiv + 479.Price f80.00.ISBN 0-471-93830-0. This book contains an interesting series of articles on both experimental and theoretical approaches to the study of gas-phase clusters. The topics chosen cover both weakly and strongly bound clusters, where ‘clusters’ range from weakly bound triatomic systems to very large assemblies. The introductory review by Kamke gives a detailed treat- ment of the photoelectron-photoion coincidence method for cluster studies. This included an extensive assessment of the experimental problems associated with such methods, with a detailed look at one of them, threshold photoelectron pho- toion coincidence, TPEPICO.In the second half of the review examples of weakly bound clusters are given. In the third chapter, by contrast, Jarrold deals with the important strongly bound class of molecules, the silicon cluster ions. He gives a comprehesive treatment of the cluster dissociation paths, of cluster structure and of reactivity. Both the articles by Lisy (Chapter 4) and the longer one by Farrar (Chapter 5) deal with the spectroscopy of solvated ions. These are studied either by the IR techniques described by Lisy or via their electronic transitions as described by Farrar. Taken together these articles give a detailed and up to date overview of this rapidly developing field. In Chapter 7 Brunetti and Vecchiocattivi, give a detailed description of both the observation of the autoionisation of collisional complexes and also of the theory used to interpret them.The complexes treated here are small ones consisting of atom-atom or atom-molecule systems, and are much smaller than those described in the rest of the reviews. The theoretical sections commence with Chapter 2 in which Lifshitz gives a detailed review of the unimolecular and collision-induced decomposition of both proton-bound and carbon-ion clusters. This is followed in Chapter 6 by a detailed review by Last and George of rare gas clusters con- taining charge atoms. In summary this series of reviews contains a wealth of information concerning the present status of cluster ions from both an experimental and a theoretical point of view.It will be very useful to anyone who wants an overview of the current status of this important field of ionised clusters. G. Duxbury Received 27th April, 1994 Applied Laser Spectroscopy. Techniques, Instrumen- tation, and Applications. Ed. David L. Andrews. VCH, Weinheim, 1992.Pp. ix + 471. Price DM 198, €81.00. ISBN 3-527-28072-3. My initial feeling before I opened this book was one of fore- boding. Here was a book with a title similar to many others that had gone before and are now long forgotten. This depression was reinforced by the publisher’s ‘blurb’ on the back cover stating that this book ‘provides a solid introduction’ to laser spectroscopy which requires no back- ground in lasers, only a general understanding of spectroscopy’.How many times does one read similar pro- mises for a book only to be disappointed? However, my initial reaction was misplaced and my fears groundless. This is a truly excellent book that lives up to its claims and even exceeds them. This is the book to give to graduate students who are about to begin a research career involving any aspect of laser spectroscopy. (In part, it has taken me so long to write this review because I have continually had to reclaim my review copy from my research students!) It would form J. CHEM. SOC. FARADAY TRANS., 1994, VOL. 90 an excellent textbook for postgraduate and post-experience courses in laser spectroscopy. Established scientists who wish to inform themselves about new developments in laser tech- nology and new techniques in laser spectroscopy will find this book invaluable.The value of the book comes from its range of coverage and the high standing of its contributors who are expert practitioners in the fields which they describe. The strength of the book undoubtedly comes from the brief given to the con- tributors by the editor that they should cover the potential and problems associated with their areas of expertise; a ‘warts-and-all’ approach that is largely ignored by most review articles, but which is most important background information for newcomers. The principles of each applica- tion are described together with the specialised instrumen- tation and illustrated with typical applications drawn from chemistry, physics and biology in both academic and com- mercial situations.The first two chapters describe the fundamental applica- tions of laser spectroscopy (Andrews) and review general aspects of laser instrumentation (McCoustra). Techniques in electronic absorption spectroscopy, multiphoton absorption spectroscopy and laser-induced fluorescence are described by Demtroder, Goodman and Philis and by Pfab, respectively. Laser methods in high-resolution IR spectroscopy are detailed by Howard and Brown. Raman spectroscopy forms the basis for two chapters; one detailing modern techniques (Morris) and the other introducing developments in non-linear Raman spectroscopy (Berger, Lavorel and Millot). Laser mass spectroscopy and its applications are reviewed by Ledingham and Singhal and the relatively new and rapidly expanding area of ultrafast spectroscopy is reviewed by Anfinrud, Johnson, Sension and Hochstrasser.The book con- cludes with an invaluable appendix detailing a wide range of laser acronyms. The editor is to be congratulated for the range of topics that have been selected giving the book a wide appeal and for persuading leading experts to write with authority. This book will remain a useful introduction to the several fields described for many years to come. It deserves a place in every science library and in the offices of research groups involved in any application of laser spectroscopy. It should be required reading for those entering into a research career involving laser spectroscopy.A case could easily be made for a low cost paperback version to be produced to make it more accessible to the people for whom it is intended and who will benefit most from it. J. C. Whitehead Received 19th May, 1994 Molecular Magnetism. By Olivier Kahn. Verlag Chemie, Weinheim, 1993.Pp. xvi + 380.Price €63.00. ISBN 3-527-89566-3. ~ ~ ~ ~~~~ The scientific potential of magnetochemistry is two-fold: on the one hand, the investigation of macroscopic magnetic properties such as magnetisation and magnetic susceptibility can serve to elucidate the microscopic, electronic and chemi- cal structure of materials, on the other hand, theoretical mag- netochemical concepts can guide synthetic attempts to control the macroscopic magnetic properties.For example, understanding the interaction of paramagnetic centres in molecular solids is of particular importance in designing new ferromagnetic materials. The interest in this problem has instigated dedicated efforts in the synthetic chemistry of coor- dination compounds of paramagnetic ions of transition metals, making it an intriguing and vigorously growing area of research. The present monograph by Olivier Kahn, himself a very active and renowned researcher in the field of molecu- J. CHEM. SOC. FARADAY TRANS., 1994, VOL. 90 lar magnetism, provides a systematic treatise of the theoreti- cal principles together with representative and illuminating experimental examples taken from current research on the magnetism of mono- and poly-nuclear transition metal com- plexes including infinite linear chains. In the words of the author, the book is primarily written to serve chemists working in the field of molecular magnetism or intending to do so.Regarding the prerequisite knowledge, the author assumes that the reader possesses a good background in sym- metry, ligand field theory and molecular orbital theory, as well as a familiarity with the operator and matrix notations used in quantum mechanics. The book is organized in 13 chapters and includes an appendix with some useful compilations of frequently required matrix representations of spin and angular momen- tum. After establishing the general relations between mag- netic susceptibility and the magnetic field dependence of molecular energy levels, the treatise starts with the consider- ation of molecules (usually coordination compounds) pos- sessing a unique magnetic centre elaborating, in succession, on cases without and with first order orbital momentum and treating the effects of zero field splitting and spin-orbit coup- ling.Two chapters are then devoted to cases of energetically close configiirations of different spin (low-spin-high-spin transition, intermediate spin, spin-admixed state). The major part of the book deals with situations where several magnetic centres interact. Since the general case of many interacting centres is systematically built on the interaction between close pairs, the situation of the two centres in a dinuclear complex is considered in detail, proceeding from isotropic interactions through the anisotropic and antisymmetric inter- actions in such systems, to the central quantum chemical models representing the present day understanding of the relation of orbital structure and spin exchange energies.One chapter then presents the methods for dealing with the new aspects and concepts arising from trinuclear complexes and compounds of higher nuclearity. This is followed by a detailed consideration of magnetic chain compounds usually built from a regular or alternating chain of magnetic metal ions connected by bridging ligands. A critical presentation of theoretical concepts and examples concerning three-dimensional magnetic ordering and the design of molecular- based magnets forms another chapter, while the final one takes up the important problem of ‘double magnetic exchange’, i.e.the combination of Heisenberg spin exchange and spin-dependent electron delocalization in mixed valence compounds. The book has been prepared with great care, although a few inevitable, usually typographical, errors have escaped the final proof reading. It is written in a very clear and rational style. The theoretical concepts are systematically developed and presented in didactically excellent fashion with efficient support by many instructive figures and diagrams. As a rule, for all the compounds discussed as examples, pertinent struc- tural information is given in graphical form.Theory and experimental examples are well balanced. This book fully achieves the author’s intent to provide a useful guide for those seeking a systematic access to the field of molecular magnetism. I find this an excellent monograph which may be expected to become a standard reference in the field. U. E.Steiner Received 13th June, 1994 Introduction to Modern Vibrational Spectroscopy. By Max Diem. John Wiley and Sons Ltd, New York, 1993. Pp. xiii + 285.Price f49.50.ISBN 0-471-59584-5. There are a number of excellent recent texts which provide an introduction to molecular spectroscopy, as well as the classic more advanced texts by Herzberg and by Wilson, Decius and Cross. However, there are few which deal comprehensively with modern vibrational spectroscopy at an introductory level.Ideally, such books should contain the theoretical back- ground necessary to understand the principles of vibrational spectroscopy, together with a description of the more impor- tant modern experimental spectroscopic techniques and com- prehensively illustrated by selected applications. To accomplish this in a text of reasonable length is a challenging task. The author has largely achieved this aim although the balance of material could perhaps be improved particularly for advanced undergraduate use. Following a short introduction, the second chapter out- lines the elementary quantum mechanical background of rotational and vibrational spectroscopy for simple molecular systems. Although limited in mathematical detail, this chapter covers most of the relevant theory required by the remainder of the text and also provides an introduction to more com- prehensive texts dealing with the quantum mechanical basis of spectroscopy.The vibrations of polyatomic molecules are treated in Chapter 3. Elementary classical and quantum treatments of vibrations in polyatomic molecules are present- ed, followed by an introduction to the theory and techniques used for the computation of vibrational frequencies and normal modes of vibration. The water molecule is used as an example, and frequencies are computed using three types of force fields. IR absorption intensities are also discussed briefly at the end of this chapter.The symmetry of molecular vibrations is introduced in the next chapter. The basic con- cepts of group theory relevant to vibrational spectroscopy are outlined in this section. This basic treatment should be sufi- cient to enable the interpretation of the vibrational spectra of many molecules and the derivation of the appropriate selec- tion rules to be carried out. In the following chapter, the theory of Raman spectroscopy is introduced. This section is well written and also contains brief accounts of resonance, non-linear and surface enhanced Raman spectroscopy. The instrumentation for both IR and Raman spectroscopy is covered in Chapter 6. A discussion of interferiometric tech- niques, including Fourier and Hadamard transforms, is included.Modern Raman instrumentation including multi- channel and Fourier transform spectrometers are described in some detail. The remaining one third of the book is concerned with applications of vibrational spectroscopy beginning with selec- ted small molecules and graduating to larger, more compli- cated, mainly biological, molecules. Considerable space is devoted to an in-depth treatment of the biological applica- tions of vibrational spectroscopy. Clearly, this is an area of major interest to the author and provides a good intro-duction to this still rapidly developing area of spectroscopy. Together with vibrational optical activity, this section occupies the major part of the section dealing with applica- tions. In an introductory text, this represents a considerable bias towards the biological area at the expense of other topics such as gas-phase or high-resolution spectroscopy which might have been included. Although vibrational optical activ- ity is also an important topic which should be included, the space devoted to this technique in a general introductory text is probably excessive. This book is accurately and well presented, and in spite of the above reservations, can be recommended as an up to date introduction to modern vibrational spectroscopy both for advanced undergraduate and postgraduate readers. The price of E49.50 for the hardcover edition is, however, too high for undergraduate purchase as a recommended text. A cheaper paperback edition would be welcome and more realistic for this sector of the market. It would also encourage graduate students to purchase the book for personal use. R. T. Bailey Received 16th June, 1994