Measurement of the Dissociation Rate of Molecular Ions


Book Description

The time interval between the ionization of a molecule by electron impact and its dissociation was determined from the kinetic energy of the fragment ions. This technique allows a direct differential sampling of the dissociation rate at various times, in contrast to previous, integral methods. The use of disc-shaped molecular beam of 28 micrometers half-width and a draw-out field of 10,000 V/cm in the ionization region resulted in a minimum measured time interval of 7.4 nonoseconds. The longest times measured were between 5 and 6 microseconds. The time dependence of the decomposition rate was measured for two decompositions in butane, five in heptane, three in benzene, one in CD4 and one in CO2(++), with rather similar results. It was established that the decay is not exponential. All decay curves, plotted semi-logarithmically, were found to have an increasing slope towards shorter times, indicating contributions from a variety of rate constants in agreement with the predictions of the statistical theory of ion decompositions.




Measurement of the Dissociation Rate of Molecular Ions


Book Description

The time interval between the ionization of a molecule by electron impact and its dissociation was determined from the kinetic energy of the fragment ions. This technique allows a direct differential sampling of the dissociation rate at various times, in contrast to previous, integral methods. The use of disc-shaped molecular beam of 28 micrometers half-width and a draw-out field of 10,000 V/cm in the ionization region resulted in a minimum measured time interval of 7.4 nonoseconds. The longest times measured were between 5 and 6 microseconds. The time dependence of the decomposition rate was measured for two decompositions in butane, five in heptane, three in benzene, one in CD4 and one in CO2(++), with rather similar results. It was established that the decay is not exponential. All decay curves, plotted semi-logarithmically, were found to have an increasing slope towards shorter times, indicating contributions from a variety of rate constants in agreement with the predictions of the statistical theory of ion decompositions.




Dissociative Recombination of Molecular Ions with Electrons


Book Description

Dissociative Recombination of Molecular Ions with Electrons is a comprehensive collection of refereed papers describing the latest developments in dissociative recombination research. The papers are written by the leading researchers in the field. The topics covered include the use of microwave afterglows, merged beams and storage rings to measure rate coefficients and to identify the products and their yields. The molecules studied range in size from the smallest, H2+, to bovine insulin ions. The theoretical papers cover the important role of Rydberg states and the use of wave packets and quantum defect theory to deduce cross sections, rate constants and quantum yields. Several theoretical and experimental papers address the controversial topic of H3+ dissociative recombination and its importance in the interstellar medium. Dissociative recombination studies of other molecular ions in the interstellar medium and in cometary and planetary atmospheres are covered. Ionization is an important competitive process to dissociative recombination and its competition with predissociation and its role in the reverse process of the association of neutral species is presented. Dissociative attachment, in which an electron attaches to a neutral molecule, has many similarities to dissociative recombination. The topics covered include the accurate calculation of electron affinities, attachment to molecules, clusters, and to species absorbed on solid surfaces and electron scattering by a molecular anion.




Dissociative Recombination


Book Description

Proceedings of a NATO ARW held in Saint Jacut de la Mer, Brittany, France, May 3-8, 1992




Kinetics of Ion-Molecule Reactions


Book Description

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.










Cluster Ions and Van Der Waals Molecules


Book Description

Smirnov (plasma chemistry, Institute of High Temperatures, Moscow) presents a comprehensive introduction to cluster ions and Van der Waals molecules for graduates and researchers in chemistry. He discusses the current ideas on the operant physics and chemistry, and reports numerical data on the parameters of the entities and processes involving them. First published in Russian in 1983. Annotation copyrighted by Book News, Inc., Portland, OR




Gaseous Molecular Ions


Book Description

Most of the matter in our solar system, and, probably, within the whole universe, exists in the form of ionized particles. On the other hand, in our natural environ ment, gaseous matter generally consists of neutral atoms and molecules. Only under certain conditions, such as within the path oflightning or in several technical devices (e. g. gas discharges, rocket engines, etc. ) will some of the atoms and molecules be ionized. It is also believed that the chemistry of the earth's troposphere predomi nantly proceeds via reactions between neutral particles. (The complex system of atmospheric chemistry will be treated in one of the forthcoming volumes to this series. ) Why, then, are ions considered so important that hundreds oflaboratories all over the world (including some of the most prestigious) are involved in research pro grams on ions, covering many different facets, from biochemistry to physics? One may obtain as many different answers as there are research groups busy in this field. There is, however, one simple, common feature which makes it attractive to work with ions: since they carry one or more net elementary charges, they can easily be gui ded, focused or separated by appropriate electric and magnetic fields, and, last but not least, they can easily be detected. Apart from these advantages, which are welcome and appreciated by the researcher, the study of molecular ions can provide insight into very fundamental aspects of the general behavior of molecules.




Ionic Liquids IV


Book Description

Ionic Liquids (ILs) are now a world-wide phenomenon and have emerged from being viewed only as novel replacements for Volatile Organic Compounds (VOCs) traditionally used as industrial solvents, into designer materials with incredible untapped potential in a wide variety of fundamental scientific and technological areas. The current series of ACS symposia dedicated to ionic liquids and the resulting books are intended to change the way people think about ionic liquids and introduce the international audience to the many new possible applications for ionic liquids. The presentations and chapters will delve more deeply into the fundamental nature of ionic liquids responsible for their fascinating behavior.