- Email: [email protected]
Time Resolved Spectroscopy
106
VlBRATIONAL
sistent use of the SI system -also I believe a matter of consensus in this day and age. Thirdly, while rightly encouraging the use of the consistant set of units and symbols, which form the main body of the manual, they do indicate that in so far as the symbols are concerned, those proposed are only IUPAC recommendations. They emphasize that other symbols or terminology may be substituted at the discretion of the author, provided that such changes are clearly defined. In many cases frequently used alternative symbols and terminology are noted and discussed in footnotes to the text. To this reviewer the inclusion of these extensive footnote commentaries is one of the most valuable features of the manual. It is one which may be sufficient to persuade the reader to change over from older non-IUPAC habits to conform with the official recommendations. In other cases the footnotes provide support, if the author has a strong preference to continue with older habits in a non-IUPAC way. R.N. Jones National Research Council of Canada Ottawa, Ontario, Canada M.J. Almond and A.J. Downs, edited by Clark and R.E. Hester, Spectroscopy of Isolated Species (Advances in Spectroscopy Vol. 17), Wiley, Chichester, 1989 (ISBN 92170-X). vi + 511 pp. Price f 111.00.
R.J.H. Matrix Series, 0-471-
Matrix isolation, originally developed by pimental, involves the trapping of short-lived or weakly bound species in an inert host at low temperatures. Since the species is isolated it may be spectroscopically examined without the need for time-resolution. The advantages of matrix isolation and its wide range of applications has led to an enormous increase in the number of papers published involving the technique, and in this volume the authors have successfully complemented and updated previous reviews on the subject. The volume includes chapters devoted to experimental techniques, energy transfer, photochemistry, low-energy species and interconversions, high-energy species, atoms and small clus-
SPECTROSCOPY
ters and astrochemistry and atmospheric processes. The selection of highlighted experiments is judicious and the text is well structured and very readable. Roughly two-thirds of the book is devoted to an extensive bibliographic survey in table form of matrix isolation covering the period 1977-86. The tables are divided into general papers, inorganic species, organometallic species, organic species and molecular complexes. Each entry summarises the preparation and spectroscopic detection of the species and includes the key findings of the study. There are 2246 references. The volume is well worth purchase by institutions which support spectroscopic research but its price (although by no means unusual) will dismay librarians in less well funded colleges. Rh. Lewis The Polytechnic of Wales Pontypridd, Great Britain R.J.H.
Clark and R.E. Hester (Eds.), Time ReSpectroscopy (Advances in Spectroscopy Series, Vol. 18). Wiley, Chichester, 1989 (ISBN O-471-92293-5). v + 406 pp. Price f. 100.00. This is the sixth single topic volume of the series that was previously entitled Advances in Infrared and Raman Spectroscopy. The volume contains a diverse collection of topics, each approaching time resolved measurements from a different perspective. The time domains discussed range from femtoseconds to seconds; the instrumentation ranges from highly sophisticated laser systems to modified “conventional” instruments. The quality of the nine individual chapters is uniformly good. The following is a brief description of each of the chapters. In Chapter one, R.J.D. Miller provides a nice overview of the use of transient gratings in spectroscopy. After presenting the various types of signals present in a grating experiment, he focusses his discussion on the thermal grating portion of the signal as a means of extracting the dynamics of non-radiative processes from chemical systems. While all the chapters in the book are quite read-
BOOK
REVIEWS
able, this one is perhaps the most lucid for the uninitiated. Both the physical and mathematical descriptions are very understandable and clearly presented. The examples focus primarily on biophysical systems. In Chapter two, L. Ziegler and co-workers use rotational Raman lineshapes and intensities to extract dynamical information. They have provided a well written resource for the theory and selection rules of resonance and hyper rotational Raman spectroscopy. This is not a chapter to be read leisurely; the interpretation of resonance rotational Raman spectra is not intuitive. The authors provide data for two chemical systems, NH, and CH,I. The last two sections of the chapter summarize the significance of the work and give a nice overview of the type of new information available with the method. This chapter will be used as a reference for resonance rotational Raman spectroscopy for some time. (This chapter also contains one of the more humorous typos on p. 69: “the conversation of angular momentum” is one I would like to hear.) In Chapter three, T. Kobayoshi and co-workers use correlation techniques and temporally incoherent nanosecond lasers to obtain ultrafast dynamics. The authors provide a theoretical framework for their work and give examples of vibrational dephasing in DMSO and optical Kerr relaxation in CS, and nitrobenzene. The authors provide a realistic comparison between their method and the direct use of femtosecond lasers to obtain the same information. Chapter four is a well written, but somewhat mistitled chapter. G.N.R. Tripathi is a pioneer in the use of transient resonance Raman spectroscopy to probe chemical radicals in solution. Justifiably, radical species are the focus of the chapter. Therefore, the author should have used the phrase “Transient Radical Intermediates” instead of “Chemical Reaction Intermediates” in the title, since “Chemical Reaction Intermediates” suggests non-radical, as well as radical species. The author summarizes the present state of understanding of the structure of many chemically important radical species and demonstrates the advantages that transient vibrational spectroscopy has over transient absorption spectroscopy in
elucidating the mechanisms and dynamics of the chemistry of radicals. In Chapter five, J.J. Sloan provides a very readable overview of methods that use Fourier transforms to do transient spectroscopy. Given the author’s experience in the area, one is left with the impression that artifacts can dominate the transient spectra obtained with these methods if great care is not exercised. The article compares the various methods and provides good insight into choosing one approach over another. There is a valuable summary of the many existing applications of the methods at the end of the chapter. In Chapter six, V. Kamalov et al. summarize their studies of the structure of the excited states of polyatomic molecules using picosecond transient coherent Raman spectroscopy (i.e., CARS and CSRS). They summarize both the advantages and disadvantages of using coherent Raman spectroscopy for these types of measurements, and they give several nice examples from their work with trans-stilbene and biomolecules. Chapters seven and eight deal with the vibrational spectroscopy of biological systems. The former, by M. Lutz and co-workers, provides an overview of the important issues in the study of the photosynthetic bacterial reaction centers; the latter, by J, Petrach and J.L. Martin, focusses on the ultrafast transient Raman spectra of hemeproteins. Both sets of authors were faced with summarizing a large amount of information, and they each succeed in the task admirably. The important issues for each of the biological systems are delineated succinctly and the contributions that transient vibrational spectroscopy has made toward solving the problems is clearly presented. The last chapter, by C.V. Shank, covers the realm of femtosecond spectroscopy. The author concentrates on the science that is accessible with femtosecond transient spectroscopy and mentions, only briefly, the details of generating and measuring these short pulses. The examples are grouped according to absorption, impulsive Raman scattering, and luminescence. The examples provide a taste of what the future holds for time resolved spectroscopy. This book is a nice addition to a well-established series. The articles are timely and well writ-
108
ten. The editors have included an appropriate selection of topics. One can sympathize with the editors having to make tough choices in the selection process. It would have been nice if the editors would have included two other chapters: one on ultrafast infrared spectroscopy and one on time resolved surface spectroscopy. These are two important areas of time resolved spectroscopy that were not addressed in detail. The lack of these two
VIBRATIONAL
SPECTROSCOPY
topics does not deter at all from the usefulness of the book; it will remain an important reference source for many years. T.L. Gustafson The Ohio State University Columbus, OH, U.S.A.
VlBRATIONAL
sistent use of the SI system -also I believe a matter of consensus in this day and age. Thirdly, while rightly encouraging the use of the consistant set of units and symbols, which form the main body of the manual, they do indicate that in so far as the symbols are concerned, those proposed are only IUPAC recommendations. They emphasize that other symbols or terminology may be substituted at the discretion of the author, provided that such changes are clearly defined. In many cases frequently used alternative symbols and terminology are noted and discussed in footnotes to the text. To this reviewer the inclusion of these extensive footnote commentaries is one of the most valuable features of the manual. It is one which may be sufficient to persuade the reader to change over from older non-IUPAC habits to conform with the official recommendations. In other cases the footnotes provide support, if the author has a strong preference to continue with older habits in a non-IUPAC way. R.N. Jones National Research Council of Canada Ottawa, Ontario, Canada M.J. Almond and A.J. Downs, edited by Clark and R.E. Hester, Spectroscopy of Isolated Species (Advances in Spectroscopy Vol. 17), Wiley, Chichester, 1989 (ISBN 92170-X). vi + 511 pp. Price f 111.00.
R.J.H. Matrix Series, 0-471-
Matrix isolation, originally developed by pimental, involves the trapping of short-lived or weakly bound species in an inert host at low temperatures. Since the species is isolated it may be spectroscopically examined without the need for time-resolution. The advantages of matrix isolation and its wide range of applications has led to an enormous increase in the number of papers published involving the technique, and in this volume the authors have successfully complemented and updated previous reviews on the subject. The volume includes chapters devoted to experimental techniques, energy transfer, photochemistry, low-energy species and interconversions, high-energy species, atoms and small clus-
SPECTROSCOPY
ters and astrochemistry and atmospheric processes. The selection of highlighted experiments is judicious and the text is well structured and very readable. Roughly two-thirds of the book is devoted to an extensive bibliographic survey in table form of matrix isolation covering the period 1977-86. The tables are divided into general papers, inorganic species, organometallic species, organic species and molecular complexes. Each entry summarises the preparation and spectroscopic detection of the species and includes the key findings of the study. There are 2246 references. The volume is well worth purchase by institutions which support spectroscopic research but its price (although by no means unusual) will dismay librarians in less well funded colleges. Rh. Lewis The Polytechnic of Wales Pontypridd, Great Britain R.J.H.
Clark and R.E. Hester (Eds.), Time ReSpectroscopy (Advances in Spectroscopy Series, Vol. 18). Wiley, Chichester, 1989 (ISBN O-471-92293-5). v + 406 pp. Price f. 100.00. This is the sixth single topic volume of the series that was previously entitled Advances in Infrared and Raman Spectroscopy. The volume contains a diverse collection of topics, each approaching time resolved measurements from a different perspective. The time domains discussed range from femtoseconds to seconds; the instrumentation ranges from highly sophisticated laser systems to modified “conventional” instruments. The quality of the nine individual chapters is uniformly good. The following is a brief description of each of the chapters. In Chapter one, R.J.D. Miller provides a nice overview of the use of transient gratings in spectroscopy. After presenting the various types of signals present in a grating experiment, he focusses his discussion on the thermal grating portion of the signal as a means of extracting the dynamics of non-radiative processes from chemical systems. While all the chapters in the book are quite read-
BOOK
REVIEWS
able, this one is perhaps the most lucid for the uninitiated. Both the physical and mathematical descriptions are very understandable and clearly presented. The examples focus primarily on biophysical systems. In Chapter two, L. Ziegler and co-workers use rotational Raman lineshapes and intensities to extract dynamical information. They have provided a well written resource for the theory and selection rules of resonance and hyper rotational Raman spectroscopy. This is not a chapter to be read leisurely; the interpretation of resonance rotational Raman spectra is not intuitive. The authors provide data for two chemical systems, NH, and CH,I. The last two sections of the chapter summarize the significance of the work and give a nice overview of the type of new information available with the method. This chapter will be used as a reference for resonance rotational Raman spectroscopy for some time. (This chapter also contains one of the more humorous typos on p. 69: “the conversation of angular momentum” is one I would like to hear.) In Chapter three, T. Kobayoshi and co-workers use correlation techniques and temporally incoherent nanosecond lasers to obtain ultrafast dynamics. The authors provide a theoretical framework for their work and give examples of vibrational dephasing in DMSO and optical Kerr relaxation in CS, and nitrobenzene. The authors provide a realistic comparison between their method and the direct use of femtosecond lasers to obtain the same information. Chapter four is a well written, but somewhat mistitled chapter. G.N.R. Tripathi is a pioneer in the use of transient resonance Raman spectroscopy to probe chemical radicals in solution. Justifiably, radical species are the focus of the chapter. Therefore, the author should have used the phrase “Transient Radical Intermediates” instead of “Chemical Reaction Intermediates” in the title, since “Chemical Reaction Intermediates” suggests non-radical, as well as radical species. The author summarizes the present state of understanding of the structure of many chemically important radical species and demonstrates the advantages that transient vibrational spectroscopy has over transient absorption spectroscopy in
elucidating the mechanisms and dynamics of the chemistry of radicals. In Chapter five, J.J. Sloan provides a very readable overview of methods that use Fourier transforms to do transient spectroscopy. Given the author’s experience in the area, one is left with the impression that artifacts can dominate the transient spectra obtained with these methods if great care is not exercised. The article compares the various methods and provides good insight into choosing one approach over another. There is a valuable summary of the many existing applications of the methods at the end of the chapter. In Chapter six, V. Kamalov et al. summarize their studies of the structure of the excited states of polyatomic molecules using picosecond transient coherent Raman spectroscopy (i.e., CARS and CSRS). They summarize both the advantages and disadvantages of using coherent Raman spectroscopy for these types of measurements, and they give several nice examples from their work with trans-stilbene and biomolecules. Chapters seven and eight deal with the vibrational spectroscopy of biological systems. The former, by M. Lutz and co-workers, provides an overview of the important issues in the study of the photosynthetic bacterial reaction centers; the latter, by J, Petrach and J.L. Martin, focusses on the ultrafast transient Raman spectra of hemeproteins. Both sets of authors were faced with summarizing a large amount of information, and they each succeed in the task admirably. The important issues for each of the biological systems are delineated succinctly and the contributions that transient vibrational spectroscopy has made toward solving the problems is clearly presented. The last chapter, by C.V. Shank, covers the realm of femtosecond spectroscopy. The author concentrates on the science that is accessible with femtosecond transient spectroscopy and mentions, only briefly, the details of generating and measuring these short pulses. The examples are grouped according to absorption, impulsive Raman scattering, and luminescence. The examples provide a taste of what the future holds for time resolved spectroscopy. This book is a nice addition to a well-established series. The articles are timely and well writ-
108
ten. The editors have included an appropriate selection of topics. One can sympathize with the editors having to make tough choices in the selection process. It would have been nice if the editors would have included two other chapters: one on ultrafast infrared spectroscopy and one on time resolved surface spectroscopy. These are two important areas of time resolved spectroscopy that were not addressed in detail. The lack of these two
VIBRATIONAL
SPECTROSCOPY
topics does not deter at all from the usefulness of the book; it will remain an important reference source for many years. T.L. Gustafson The Ohio State University Columbus, OH, U.S.A.