Introduction to modern vibrational spectroscopy

Introduction to modern vibrational spectroscopy

XIV trends in analytical chemistry, vol. 14, no. 2, 1995 Owed to spectroscopists past (and present) lntroduc tion to Modern Vibrational Spectroscopy...

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trends in analytical chemistry, vol. 14, no. 2, 1995

Owed to spectroscopists past (and present) lntroduc tion to Modern Vibrational Spectroscopy by Max Diem, 1993, Wiley, Chichester, price f49.50 (xiv + 286 pages), ISBN O-471-5958-5 When I received my review copy of Introduction to Modem Vibrational Spectroscopy by Professor Max Diem,

I was struck by its physical resemblance to an earlier molecular spectroscopy text, Introduction to Molecular Spectroscopy, by Gordon Barrow. Not only are the titles similar, but the books are similarly sized and comparably thin, having light-colored covers with vibration-rotation spectra upon them (albeit of different molecules) . This theme, relating to the influence of previous works in molecular spectroscopy (and quantum chemistry) upon the current book, is continued upon opening the text and exploring the material inside. In fact, Professor Diem readily acknowledges the sway that the classic books by Herzberg (Infrared and Raman Spectra of Polyatomic Molecules) and Wrlson, Decius and Cross (Molecular Mbrations) have had upon the field of molecular spectroscopy and his own understanding of the topic. After an introductory chapter, Modem Vibrational Spectroscopy continues with an obligatory “skirmish” (a la Harris and Bertolucci) with quantum mechanics, a discussion based upon I. N. Levine’s two volumes Quantum Chemistry and Molecular Spectroscopy. Chapter 3, owing much to Wilson, Decius and Cross, develops the theory behind the vibrational spectra of polyatomic molecules. Chapter 4, harking to Cotton’s book, describes the applications of symmetry and group theory in vibrational spectroscopy. An introduction to Raman spectroscopy is provided in Chapter 5, and while Koningstein’s 1972 book on the theory of Raman spectroscopy is cited, no mention of Placzek’s much earlier, pioneering work in this field is provided. On the other hand, a nice feature of this present text is that resonance Raman spectroscopy is discussed, as are the many modern Raman offshoots, such as the inverse and hyper Raman effects, as well as those typically abbreviated:

SERS, CARS, RIKES, and so forth. Another very useful feature of Diem’s book is that both instrumentation for vibrational spectroscopy and some sampling techniques are presented in Chapter 6. Dispersive and interferometric instruments are discussed, although, oddly enough, no citations are given to the “bibles” on Fourier transform infrared spectrometry by Peter Griffiths and Griffiths and de Haseth. Furthermore, only a limited set of sampling techniques is given; no mention is made of modern, hyphenated techniques coupling chromatography with vibrational spectroscopy, for example. Interestingly, Hadamard transform spectroscopy is also mentioned, but briefly. Chapter 7 (in a similar vein as Herzberg) provides a detailed discussion of the assignment of observed spectral bands to molecular vibrational modes. Contrary to Herzberg, however, the spectra themselves are not used to deduce molecular structure, which is, instead, deduced from VSEPR and similar arguments. Starting with triatomic molecules, the author takes us on a tour of the vibrational spectra of ever-larger moleconsidering spherical, cules, symmetric, and asymmetric stops along the way. A look at the vibrational spectra of benzene and alanine (to set the stage for a later discussion of larger biomolecules) concludes this chapter. The final two chapters explore two aspects of modern vibrational specand reflect Professor troscopy, Diem’s own research interests. A discussion of the vibrational spectroscopy of peptides and proteins, nucleic acids and lipids neglects only the carbohydrates as a class of biomolecules of spectroscopic interest. Chapter 9 focuses upon vibrational circular dichroism (VCD) and Raman optical activity (ROA). Both of these chapters include recent references to work by most of the major players in these fields. Conspicuously absent, however, are citations of the work of G. J. Thomas, Jr. in nucleic acid Raman spectroscopy (although he is referenced under protein spectroscopy), and I! J. Stephens under VCD. Three appendices - on group frequencies, Urey-Bradley force constants, and

character tables - and a useable index complete the text. Technically, this book is quite well done; it is well-written and largely free of obvious typographical errors. A cursory inspection of the book’s equations, however, revealed that Equation 2.7.4, for instance, contains an extra factor oflyn(z) - somethingthat would be picked up by the very good student (and; hopefully, the instructor!), but which would be likely to cause considerable consternation on the part of the weaker student. Overall, I have three additional recommendations which I would have liked to have seen incorporated into the present edition of Introduction to Modem



First of all, homework questions should have been provided; these would be helpful not only to the student in understanding the concepts presented in the various chapters, but also for instructors potentially considering adoption of the book. Secondly, a tenth chapter would have been nice, one which at least identifies and summarizes many more of the truly modern applications of vibrational spectroscopy beyond the author’s personal biases. For example, hyphenated techniques, two-dimensional IR, vibrational spectroscopy of advanced materials such as high Tc superconductors, and vibrational excited states and vibrational dynamics would all be appropriate for the title of this text, as would many other topics which could easily be found in the meeting proceedings from recent international conferences on Raman spectroscopy and Fourier transform spectroscopy. Finally, the author seems to dismiss both vibrational analysis and the application of computational methods (both ab initio and semi-empirical) to interpreting vibrational spectra. He implies that all of the “low-hanging (spectroscopic) fruit” has already been plucked, and that computational methods may not be useful for molecules containing more than 10-12 atoms. I can personally assure him that both areas of vibrational research are definitely active and “modern.” In all, any book which closely parallels the lecture notes I use for my own senior/graduate level course in mole-

trends in analyticalchemisfv, vol.14, no.2, 1995

cular spectroscopy has a lot to recommend it. In spite of our markedly different backgrounds and training in the area of vibrational spectroscopy, both Professor Diem and I stand on the shoulders of those who have gone before us, and this book can be considered to be a tribute to the pioneering efforts of people like Herzberg or Wilson, Decius and Cross, and the many others who have laid the groundwork for modern vibrational

xv spectroscopy. Given the paucity of textbooks for courses in molecular spectroscopy (although there are plenty of monographs on “selected topics” in this field) I would give Professor Diem’s Introduction to Modem I/ibrational Spectroscopy serious consideration for use in my own class - even though it does not cover rotational, electronic or magnetic spectroscopies. With this proviso, and those noted above, I

would also recommend leagues.

it to my col-

CHARLES C. WURREY Professor C.J. Wurrey is at the Department of Chemistry, University of Missouri-Kansas City,5100 Rockhill Road, Kansas City, Missouri 64110-2499, USA.

Computers for laboratory automation The Use of Computers for Laboratory Automation, by S.P Maj, Royal Society of Chemistry Cambridge, 1993, price f22.50 (xviii + 358 pages), ISBN O-85186-744-8 The book comprises chapters that provide an introduction to communication with the computer, data representation, microprocessors, memory devices, operating systems, input and output interfacing, networking, data processing, software engineering and Laboratory Information Manage-

to consult additional references before all questions are answered or a thorough understanding is gained. Particular attention is given to LIMS, and to the problems associated with the use, verification, and validation of computers in regulated environments.

ment based Systems (LIMS). A bibliography and index are included. The book concentrates mainly on a number of general aspects of automation and could be extended to give a detailed approach to automation problems. It places the emphasis on principles of operation rather than on product-specific details. It is a helpful complementary text, and is most suited for reading in an academic postgraduate environment. The coverage of most topics is too abbreviated for it to serve as a textbook. For many topics, one will need

V CERD/\ Dr V Cerdci is at the Association of Environmental Sciences, Department of Chemistry, Universitat de les Illes Balears, E-07071 Palma de Mallorca, Spain.

ation techniques. Molecular weight determinations are covered in Chapter 8 while Chapter 9 covers copolymer composition measurements and Chapter 10 polymer microstructure. Chapters 11-13 deal with the thermal methods for determining the transitional behaviour of polymers. The book is a mass of detail and description of literary hundreds of practical tests for polymer analysis. To say that it is encyclopedic in detail is no understatement. Yet the introductory material and transitional discussions from one subject to another are well written in a terse but authorative style. The book is more of a source book than an educational tool and many people will appreciate having, in one place, such a collection of tests. Unfortunately, the index is totally inadequate for an 800 page book but the extensive table of contents compensates somewhat when one is looking for a particular method or polymer system. There are 2367 references at the end of the book which is

highly commendable. It may appear to be egotistical but here I found my name spelled with four different variations (ref. 123, Keonig, J.L.; ref. 124, Koenig, J.L.; ref. 1410 Kownig, J.L.; ref. 1756, Koenig, S.L.) and citations with my name attached which were new to me. These kinds of errors tend to allow some concern to creep in about the accuracy of the other references. There appear to be no references later than 1988 (Oops, I found one for 1989). But, in general, the descriptions of the methods in the book are sufficiently complete to negate the need to turn to the original references. Some of the tables are not practically useable, i.e. Table 17 p 102 where the script is too small to read. There are some irritating things in the book. Why describe IR methods based on salt prism spectrometers when almost no dispersive instruments exist anymore - FIIR has replaced them. To report the wavelengths in microns rather in the energy units of wave numbers is also

Practical polymer analysis Practical Polymer Analysis, by bR. Crompton, Plenum Press, London, 1993 (xx + 810 pages), f 140, US$ 175, ISBN: o-306-44524-7 The author indicates that the purpose of this book is “to familiarize the reader with the practical aspects of polymer analysis”. To this end, the book describes many methods of analysis and provides extensive tables and diagrams covering the practical aspects of polymer analysis. Chapters 1 and 2 are introductory in nature and in Chapter 3, the separation methods are described and practical examples of such separations are given. Chapter 4 illustrates the tests for polymer identification, ranging from simple physical tests to fingerprinting techniques and including spectroscopic techniques. Chapter 5 focuses on additive and contamination analysis techniques. Chapter 6 examines the tests for functional groups in polymers. Chapter 7 covers fraction-