Recent advances in both experimental techniques and theoretical methodologies have meant that increasingly sophisticated studies concerning the formation, structures, energetics, and reaction dynamics of state- or energy-selected molecular ions can now be performed. In order to better serve the ion chemistry and physics community, each volume of this series will be dedicated to reviewing a specific topic, emphasizing new experimental and theoretical developments in the study of ions. The Wiley Series in Ion Chemistry and Physics will help stimulate new research directions and point to future opportunities in the field of ion chemistry and physics. This fourth volume is devoted to developments associated with the high resolution study of molecular photoionization, presented from both experimental and theoretical viewpoints. This field has been revolutionized in recent years through the rapid development of zero kinetic energy (ZEKE) photoelectron spectroscopy, which is featured prominently within this volume. These advances have expanded the researcher' s ability to probe not just structural features, but also the detailed dynamics of a system, resulting in the interest and applicability of the technique being broadened to areas of chemical physics extending beyond the traditional study of photoionization per se. Each of the twelve chapters making up this volume is written by leading researchers in their respective fields.

The main goal of this research program was to obtain accurate thermochemical and spectroscopic data, such as ionization energies (IEs), 0 K bond dissociation energies, 0 K heats of formation, and spectroscopic constants for radicals and molecules and their ions of relevance to combustion chemistry. Two unique, generally applicable vacuum ultraviolet (VUV) laser photoion-photoelectron apparatuses have been developed in our group, which have used for high-resolution photoionization, photoelectron, and photodissociation studies for many small molecules of combustion relevance.

Owing to the advances of vacuum ultraviolet and ultrafast lasers and third generation synchrotron sources, the research on photoionization, photoelectrons, and photodetachment has gained much vitality in recent years. These new light sources, together with ingenious experimental techniques, such as the coincidence imaging, molecular beam, pulsed field ionization photoelectron, mass-analyzed threshold ion, and pulsed field ion pair schemes, have allowed spectroscopic, dynamic, and energetic studies of gaseous species to a new level of detail and accuracy. Profitable applications of these methods to liquids are emerging.This invaluable two-volume review consists of twenty-two chapters, focusing on recent developments in photoionization and photodetachment studies of atoms; molecules, transient species, clusters, and liquids.

Single-photon vacuum ultraviolet (VUV) and two-color laser photoionization and pulsed field ionization-photoelectron (PFI-PE) measurements have been applied to the studies of transient radicals and metal-containing molecules generated by various in situ production schemes. Phenoxyl radical (C6H5O) has been prepared by flash pyrolysis of allyl phenyl ether in a hyperthermal pyrolysis nozzle of the Chen design. A Smalley-type ablation source has been installed and developed for the production of diatomic iron carbide (FeC) for two-color laser excitation-photoionization experiment. Sulfur monoxide radical (SO) has been prepared by using a supersonically cooled radical beam source based on the 193 nm excimer laser photodissociation of SO2. Based on the simulation of the rotational structures resolved in the PFI-PE bands of these species, highly accurate ionization energies (IEs) and spectroscopic constants are determined. These values are compared to IEs predicted by high-level ab initio quantum chemical calculations using the wave function based CCSDTQ(Full)/CBS approach (and its variations), which involves the approximation to the complete basis set (CBS) limit at the coupled cluster level up to full quadruple excitations. By benchmarking theoretical predictions with experimental results, a wide applicability of the CCSDTQ(Full)/CBS procedure in quantum chemical calculations of molecular energetic and spectroscopic properties have been demonstrated.

This book celebrates the career and scientific accomplishments of Professor David Buckingham, who is due to retire from his Chair at Cambridge University in 1997. The adopted format comprises reprints of a number of David Buckingham's key scientific papers, each one or two of these preceded by a review of the corresponding area of David's wide-ranging research interest. Each reviewer is recognised as an expert in that field of interest and has some close association with David Buckingham, as a scientific colleague and/or a former research student. The book should serve as a distinctive reference source, both retrospective and prospective, for the field of chemical physics with which the name A.D. Buckingham is associated. The editors opted to reprint a majority of early classic Buckingham papers, balanced by some of David Buckingham's more recent publications. Reprinted papers have been placed into a general scientific context that covers prior influences on, and later impacts by, the work nominated for review.