The book brings together, for the first time, all aspects of reactions of metallic species in the gas phase and gives an up-to-date overview of the field. Reactions covered include those of atomic, other free radical and transient neutral species, as well as ions. Experimental and theoretical work is reviewed and the efforts to establish a closer link between these approaches are discussed. The field is mainly approached from a fundamental point-of-view, but the applied problems which have helped stimulate the interest are pointed out and form the major subject of the final chapters. These emphasize the competition between purely gas-phase and gas-surface reactions.

The chapters in this book are devoted to the elementary reactions of small molecules in the gas phase, with some emphasis on reactions important in combustion. The first three chapters cover experimental measurements made at high temperatures, mainly using shock waves and flames; the final chapter describes discharge flow methods near room temperature. The authors-all active in the fields they describe were asked to aim at a level intermediate between a textbook and a review, designed for readers not already familiar with this branch of chemical kinetics. We hope the book will prove especially useful to research workers in related subjects, to research students, and perhaps as source material for the preparation of lectures. The examples have been chosen to illustrate the theoretical basis of the topics rather than attempt a complete coverage. Professors Wagner and Troe describe the remarkable progress made in recent years in measuring dissociation rates for small molecules. Tests ofunimolecular reaction theories are usually made in the 'fall-off' region of pressure: the kinetics change from first order to second order as the pressure is reduced. For large molecules this region lies below atmospheric pressure and is relatively easily accessible. For molecules with four or less atoms, however, the fall-off region lies well above atmospheric pressure: it has been explored using the high pressure shock tube techniques developed by the authors.

The present monograph appears after the death of Professor V. N. Kondratiev, one of those scientists who have greatly contributed to the foundation of contem porary gas kinetics. The most fundamental idea of chemical kinetics, put for ward at the beginning of the twentieth century and connected with names such as W. Nernst, M. Bodenstein, N. N. Semenov, and C. N. Hinshelwood, was that the complex chemical reactions are in fact a manifestation of a set of simpler elementary reactions involving but a small number of species. V. N. Kondratiev was one of the first to adopt this idea and to start investigations on the elementary chemical reactions proper. These investigations revealed explicitly that every elementary reaction in turn consisted of many elementary events usually referred to as elementary processes. It took some time to realize that an elementary reaction, represented in a very simple way by a macroscopic kinetic equation, can be described on a microscopic level by a generalized Boltzmann equation. Neverheless, up to the middle of the twentieth century, gas kinetics was mainly concerned with the interpretation of complex chemical reactions via a set of elementary reactions. But later on, the situation changed drastically. First, the conditions for reducing microscopic cquations to macroscopic ones were clearly set up. These are essentially based on the fact that the small perturbations of the Maxwell-Boltzmann distribution are caused by the reaction proper.

The report very briefly covers the following: Atom-molecule and ion-molecule reactions in flow systems; 58.4 nm photolyses of small molecules and the fluorescence of excited molecular ions generated during such photolyses; phase-shift studies of excited atom reactions; and matrix isolation spectroscopy.

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.