The use of supersonic molecular beams in photoionization mass spectroscopy and photoelectron spectroscopy to assist in the understanding of photoexcitation in the vacuum ultraviolet is described. Rotational relaxation and condensation due to supersonic expansion were shown to offer new possibilities for molecular photoionization studies. Molecular beam photoionization mass spectroscopy has been extended above 21 eV photon energy by the use of Stanford Synchrotron Radiation Laboratory (SSRL) facilities. Design considerations are discussed that have advanced the state-of-the-art in high resolution vuv photoelectron spectroscopy. To extend gas-phase studies to 160 eV photon energy, a windowless vuv-xuv beam line design is proposed.

Photoabsorption, Photoionization, and Photoelectron Spectroscopy explores photoabsorption processes involving individual, isolated molecules in the wavelength or photon energy range from the ionization thresholds of molecules (usually in the vacuum ultraviolet region) through the soft and hard X-ray region and beyond the ""K edge."" The interaction between electromagnetic radiation and isolated molecules based on photoabsorption, photoionization, and photoelectron spectroscopy studies is described, along with the techniques for measurement of total and partial cross sections. This book is comprised of eight chapters and examines the decomposition of molecules and molecular ions as well as mildly excited (valence shell excitation) and highly excited (inner shell excitation) molecules. After providing a general theoretical background, it discusses certain classes of atoms and molecules and considers electromagnetic interactions with gases. The following chapters focus on photoabsorption below the first ionization limit; quasi-discrete states above the first ionization potential; and the ionization continuum. Total photoabsorption and photoionization cross sections for selected molecules are also considered, and the angular distribution of photoelectrons is analyzed. The various measurement techniques are described in the last chapter. This monograph will be of interest to radiation chemists, radiation physicists, photochemists, mass spectrometrists, and perhaps radiation biologists.

Ultraviolet Photoelectron and Photoion Spectroscopy, Auger Electron Spectroscopy, Plasma Excitation in Spectrochemical Analysis

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.

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.

Rasmus Brogaard's thesis digs into the fundamental issue of how the shape of a molecule relates to its photochemical reactivity. This relation is drastically different from that of ground-state chemistry, since lifetimes of excited states are often comparable to or even shorter than the time scales of conformational changes. Combining theoretical and experimental efforts in femto-second time-resolved photoionization Rasmus Brogaard finds that a requirement for an efficient photochemical reaction is the prearrangement of the constituents in a reactive conformation. Furthermore, he is able to show that by exploiting a strong ionic interaction between two chromophores, a coherent molecular motion can be induced and probed in real-time. This way of using bichromophoric interactions provides a promising strategy for future research on conformational dynamics.