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Book Review Ion and Cluster Ion Spectroscopy and Structure. Edited by J. P. Maier

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Chapter 3 discusses detectors based on the reaction of NO
with ozone. A post column reactor is used to generate NO by
a reaction of the analyte; ozone is then added downstream
and the chemiluminescent emission measured. The first such
system is specific for N-nitroso compounds which undergo
catalyzed pyrolysis to form NO. Specificity for nitrogen
compounds is obtained by catalytic oxidation of the effluent
with O,, since only nitrogen compounds form NO. A general
detector is obtained by use of NO, as a reagent, which reacts
with most analytes on a hot gold surface to yield NO.
HPLC detection based on solution-phase chemiluminescence is discussed in Chapter 4. Systems include luminol,
lucigenin, peroxyoxalates, tris(2,2'-bipyridine)rutfienium(11),
electroluminescence, and luciferin. One, or sometimes two,
post-column reagent-introduction systems are used. The
analytes may be catalysts which stimulate emission, or catalyst suppressors which lower emission levels. Labeling the
analytes with, for example, luminol is also discussed. The
entirety of Chapter 5 is devoted to the peroxyoxalate chemiluminescence reaction ; the mechanism and kinetics of the
process are reviewed. Hydrogen peroxide reacts with one of
several aryl oxalate esters to produce an energetic intetmediate, which then reacts with an acceptor (fluorophore) from
which the actual light emission occurs. Hydrogen peroxide
and certain classes of organic fluorophores can be detected.
Photochemical reaction HPLC detection is reviewed lucidly in Chapter 6. The introductory sections of this chapter
present the limitations of HPLC detectors currently in use,
the rationale for use of photochemical detectors of generally
greater complexity, and the effect of post-column reactors on
chromatography. This may be the best chapter in the book
for the scientist unfamiliar with this field since it clearly
delineates why anyone would bother with these rather complex systems and gives a good overview of their limitations as
well as their advantages.
Chapter 7 discusses the use of singlet oxygen sensitization,
by which the authors mean analyte-induced photooxidation
of a singlet oxygen acceptor which has been spiked into the
HPLC mobile phase. Here, the change in UV absorption
caused by the photooxidation reaction is monitored. In favorable cases, detection limits are improved by 10-100 fold
over usual UV detection.
The book is attractively produced, thoroughly referenced,
and appears to be free of errors. It is recommended to anyone interested in the subject matter.
Wilson M . Gulick, Jr. [NB 1050 IE]
College of Engineering
Michigan Technological University
Houghton, MI (USA)
Ion and Cluster Ion Spectroscopy and Structure. Edited by
J. P. Maier. Elsevier, Amsterdam 1989. xiv, 484 pp., hardcover, DFI. 330.00.ASBN 0-444-87283-3
This book provides the reader with in depth and up to date
knowledge concerning various aspects of the physics and
chemistry of ions (including cluster ions). In particular this
book, written by several leaders in their respective fields,
aims to cover the subject of photon-ion interaction (spectroscopy, photodissociation and photodetachment). In addition,
Coulomb explosion, high pressure mass spectrometry and
metastable fragmentations are discussed as methods to elucidate the structure of ions. Some of the chapters are written
very well, are based on a large basis of new and interesting
Angew. C'hrm lnt. Ed. Engl. 29 (1990) No. 4
findings and constitute hoped-for first competent reviews on
these subjects.
The book starts with a chapter (2. Vager, R. Naaman,
E. P. Kanter) describing a new approach to the study of
molecular structure--Coulomb Explosion Imaging-and
its application to systems where classical spectroscopic methods are limited, i.e. non rigid molecules and molecular ions.
This is followed by a chapter ( R . C. Woods) on recent advances in microwave spectroscopy, including details of (23)
molecular ions studied so far and their detection in interstellar space by radioastronomy. Chapter 3 (P. Botschuina) provides a review on spectroscopic properties obtained by the
author for molecular ions with up to 7 nuclei. Special emphasis is given to effects of vibrational anharmonicity. Chapter 4
( H . E Schaefer ZZI) and Chapter 5 (J. V: Coe, R. J. Saykally)
demonstrate the profitable alliance between a theoretical
and an experimental group in order to unravel the infrared
spectra of 6 polyatomic molecular ions ( H 3 0 + , NHJ,
H,CH+, HCO: , HN,O+, C,H:). Besides a brief chronology Saykally et al. describe several new developments in the
field of high resolution infrared laser molecular ion spectroscopy. Chapter 6 (D. M . Neumark) discusses high resolution
photodetachment studies, including both direct photodetachment and autodetachment spectra of molecular negative
ions. Chapter 7 (J. P. Maier) consists of current progress in
the characterization of open-shell cations by means of their
electronic transitions. As an example, the B4 CU--8"Cg-transition of C t is discussed in detail, demonstrating the first
successful probing of a fragment ion.
Chapter 8 through 13 deal with the rapidly growing field
of cluster ions. This part of the book starts with a Chapter
( R . A . Kennedy, C. Y Kung, 7: A . Miller) describing a prototype instrument in which cluster ions are analysed by time of
flight mass spectrometry after spectroscopic probing by laser
induced fluorescence. Chapter 9 ( M . 7: Bowers) gives a comprehensive overview on the photodissociation dynamics of
small cluster ions (21 dimers and trimers). These studies yield
information on the location and nature of the electronic
excited states, on product branching ratios and product energy disposal. Chapter 10 ( R . G. Keesee, A. W: Castleman, Jr.)
summarizes the importance of thermochemical data for inferring structural information of solvated cluster ions and
demonstrates the supportive role of adequate calculations
concerning cluster ion stability. Moreover, this chapter also
contains new results from photodissociation, unimolecular
and collision induced dissociation of cluster cations. Chapter 11 ( N . Heinrich, H. Schwarz) contains an essay demonstrating the intriguing gas phase chemistry of metastable
cations of some keto/enol tautomers using recent experimental and theoretical data. It is postulated that loosely bound
H-bridged ion/dipole complexes have to be seen as central
intermediates in the low energy metastable ion decomposition of these ions. The remaining two chapters by R. E.
Smalley and coworkers and K. H . Bowen and coworkers deal
with the recent development of cluster anion photodetachment spectroscopy, using pulsed cluster ion sources and continuous cluster ion sources, respectively. These methods permit the study of ultraviolet photoelectron spectra of virtually
any cluster of any element or combination of elements.
This book constitutes a valuable source of reference in the
rapidly expanding topic of ion physics and chemistry and
appears to be a must for every scientist working in the field
of molecular and cluster ions
cj VCH VL.riug.~~eseii.~chufi
m b H , 0-6940 Weinheim, 1990
7: D. Murk [NB 1025 IE]
Institut fur Ionenphysik
Universitat Innsbruck (Austria)
0570-0833/90j0404-0437 $02.50/(1
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spectroscopy, structure, clusters, ion, book, maier, edited, review
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