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The first comprehensive collection of all the major techniques used to study gas phase interactions is presented in this volume. With complete coverage of what a given technique can accomplish, its advantages and disadvantages, the book is designed to teach advanced students and researchers entering the field how to investigate a broad range of topics. Included is coverage of traditional topics such as ion cyclotron resonance, as well as more recent innovations, including Fourier transform mass spectrometry and ionic cluster studies. Several diagrams of instrumentation and examples of experimental data are also provided.
After a few faint stirrings of interest in ion-molecule reactions during the early days of mass spectrometry, the subject was almost completely neglected for many years. There was a renascence of interest in the subject following pioneering experiments by Tal'roze in Russia and independently by Steven son and Schissler and Field, Franklin, and Lampe in this country. Since that time, interest in the subject has continued to grow and the number of papers published to expand almost exponentially during the past 15 years. The result is a body of literature that is now almost beyond any single individual's capacity for encompassing in his reading and research activities. Thus, it seemed timely to prepare a book giving in some detail a comprehen sive review of the field. Ideally, such a book would be written by one or possibly two authors. Unfortunately, the sheer bulk and variety of the studies of ion-molecule reactions has made it impractical for a single person to prepare a book on the subject in a time that would permit it to be issued before the material covered was obsolete. Consequently, the only practical, although surely not the ideal, solution is to issue a multiauthor volume. The present book represents our best efforts to accomplish this goal. We have secured from 18 authors material representing the most advanced work in the field and the resulting compilation is presented herein.
Gas Phase Ion Chemistry, Volume 2 covers the advances in gas phase ion chemistry. The book discusses the stabilities of positive ions from equilibrium gas-phase basicity measurements; the experimental methods used to determine molecular electron affinities, specifically photoelectron spectroscopy, photodetachment spectroscopy, charge transfer, and collisional ionization; and the gas-phase acidity scale. The text also describes the basis of the technique of chemical ionization mass spectrometry; the energetics and mechanisms of unimolecular reactions of positive ions; and the photodissociation of gas-phase ions. The applications of molecular beam techniques to the study of ion-molecule collisions; as well as the variational treatment of charge transfer reactions are also encompassed. Chemists and biochemists will find the book invaluable.
This book explores the mechanism of alkali-metal ion/molecule association reaction, surveys the instrumental basis to study its kinetic, and describes the instrumentation to the measurement of alkali-metal ion affinities. The applications of the ion complexation mechanism in the condensed phase in reaction to direct analysis MS are also covered. Other topics include mechanism and reaction rate, experimental and theoretical ion affinities, applications of ion attachment reactions (IAR) to mass spectrometry such as alkali ion CIMS, ion attachment MS and cationization mass spectrometry of ESI, FAB, FD, LD, MALDI and SIMS and topics of IAR-based direct analysis mass spectrometry.
Of Volume 2.- 8. Flowing Afterglow Studies.- 1. Introduction.- 2. Studies Bearing on Intermediate Complex Formation in Thermal Energy Collisions.- 2.1. Temperature Dependence of Slow Ion-Molecule Reactions.- 2.2. Three-Body Reaction Rate Constants.- 2.3. Rotational Excitation in Ion-Neutral Reactions.- 2.4. Miscellaneous Considerations of Intermediate Complex Processes.- 3. Studies Bearing on Negative-Ion Resonance Formation.- 4. Studies Bearing on Energetics.- 5. Conclusions.- References.- 9. Ion Cyclotron Resonance Spectrometry.- 1. Introduction.- 1.1. General Characteristics.- 2. Theoretica.
The investigation of the elementary reactions of reactive intermediate species began about half a centruy ago with the advent of free radical kinetics as an active area of chemical research. In spite of the relatively greater ease of detection of a species carrying an electrical charge, and the fact that organic chemists had for decades postulated mechanisms involving ionic intermediates, the systematic study of the elementary reactions of ions was delayed for more than twenty years after the first beginnings of free radical kinetics. Even at this writing, in 1978, the word "kinetics" is considered by many chemists to be synomomous with "kinetics of neutral species". Yet in spite of the relatively late start and separation from the mainstream of kinetics, the field of ion physics and chemistry is fluorishing, and growing at an ever faster pace. Instrumentalists devise ever more sophisticated apparatuses with capabilities of delving into nearly every aspect of the interactions between ions and molecules. Even satellites orbiting the earth are now being used effectively to determine rate coefficients of ionospheric ion-neutral reactions, some of which can not as yet be measured in the laboratory.