Photodissociation Spectroscopy and Dynamics of Free Radicals, Clusters, and Ions


Book Description

The photodissociation spectroscopy and dynamics of free radicals and ions is studied to characterize the dissociative electronic states in these species. To accomplish this, a special method of radical production, based on the photodetachment of the corresponding negative ion, has been combined with the technique of fast beam photofragment translational spectroscopy. The photofragment yield as a function of photon energy is obtained, mapping out the dissociative and predissociative electronic states. Branching ratios to various product channels, the translational energy distributions of the fragments, and bond dissociation energies are then determined at selected photon energies. The detailed picture of photodissociation dynamics is provided with the aid of ab initio calculations and a statistical model to interpret the observed data. Important reaction intermediates in combustion reactions have been studied: CCO, C2H5O, and linear C{sub n} (n = 4--6).
















Studies of Transition States, Clusters, and Radicals by Negative Ion Photodetachment and Photodissociation


Book Description

Our AFOSR-supported research during the last three years focused on several experimental programs at the interface of ion spectroscopy and molecular reaction dynamics. We have developed a new method for high resolution photodetachment spectroscopy of negative ions based on photoelectron imaging (SEVI, or Slow photoElectron Velocity-map Imaging) and applied it to simple test systems as well as a pre-reactive van der Waals complex. We have measured photoelectron spectra of solvated transition state precursor anions, and used the vibrational structure in these spectra to infer to effect of various solvents on the strong hydrogen bond in the anion core. This work led to a series of experiments in which we measured the infrared spectra of several strongly hydrogen-bonded anions and the protonated water dimer H5O2+. These experiments were performed on the Free Electron Laser for Infrared experiments (FELIX) which produces high power, tunable infrared pulses over a broad spectral range, enabling the first measurements of the low (







Reaction Dynamics in Clusters and Condensed Phases


Book Description

The Twenty Sixth Jerusalem Symposium reflected the high standards of these distinguished scientific meetings, which convene once a year at the Israel Academy of Sciences and Humanities in Jerusalem to discuss a specific topic in the broad area of quantum chemistry and biochemistry. The topic at this year's Jerusalem Symposium was reaction dynamics in clusters and condensed phases, which constitutes a truly interdisciplinary subject of central interest in the areas of chemical dynamics, kinetics, photochemistry and condensed matter chemical physics. The main theme of the Symposium was built around the exploration of the interrelationship between the dynamics in large finite clusters and in infinite bulk systems. The main issues addressed microscopic and macroscopic sol vation phenomena, cluster and bulk spectroscopy, photodissociation and vibrational predissociation, cage effects, interphase dynamics, reaction dynamics and energy transfer in clusters, dense fluids, liquids, solids and biophysical systems. The interdisciplinary nature of this research area was deliberated by intensive and extensive interactions between modern theory and advanced experimental methods. This volume provides a record of the invited lectures at the Symposium.




Photoionization and Photodetachment


Book Description

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.