Advances in Chemical Reaction Dynamics


Book Description

This book contains the formal lectures and contributed papers presented at the NATO Advanced Study Institute on. the Advances in Chemical Reaction Dynamics. The meeting convened at the city of Iraklion, Crete, Greece on 25 August 1985 and continued to 7 September 1985. The material presented describes the fundamental and recent advances in experimental and theoretical aspects of, reaction dynamics. A large section is devoted to electronically excited states, ionic species, and free radicals, relevant to chemical sys tems. In addition recent advances in gas phase polymerization, formation of clusters, and energy release processes in energetic materials were presented. Selected papers deal with topics such as the dynamics of electric field effects in low polar solutions, high electric field perturbations and relaxation of dipole equilibria, correlation in picosecond/laser pulse scattering, and applications to fast reaction dynamics. Picosecond transient Raman spectroscopy which has been used for the elucidation of reaction dynamics and structural changes occurring during the course of ultrafast chemical reactions; propagation of turbulent flames and detonations in gaseous· energetic systems are also discussed in some detail. In addition a large portion of the program was devoted to current experimental and theoretical studies of the structure of the transition state as inferred from product state distributions; translational energy release in the photodissociation of aromatic molecules; intramolecu lar and intraionic dynamic processes.




The Chemical Dynamics and Kinetics of Small Radicals


Book Description

This book highlights recent progress in the chemistry of radicals. Developments include the growing use of lasers to generate radicals, the application of lasers to provide state, angular, polarization, energy and real-time resolution in kinetics and dynamics experiments, the development of theories for handling the reactions of radicals, and the simulation of the reaction dynamics of increasingly larger systems for direct comparison to experimental results. The book emphasizes the increasing interaction between experimental dynamics, kinetics and theory. It is appropriate for chemistry graduate students and researchers about to enter the field. However, the discussions of some topics progress to a more advanced level so that even an expert will find the book useful.




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.




The Chemical Dynamics and Kinetics of Small Radicals


Book Description

This book highlights recent progress in the chemistry of radicals. Developments include the growing use of lasers to generate radicals, the application of lasers to provide state, angular, polarization, energy and real-time resolution in kinetics and dynamics experiments, the development of theories for handling the reactions of radicals, and the simulation of the reaction dynamics of increasingly larger systems for direct comparison to experimental results. The book emphasizes the increasing interaction between experimental dynamics, kinetics and theory. It is appropriate for chemistry graduate students and researchers about to enter the field. However, the discussions of some topics progress to a more advanced level so that even an expert will find the book useful.




Reaction Dynamics


Book Description

During the last 30 years our knowledge and understanding of molecular processes has followed the development of increasingly sophisticated tech niques for studying fast reactions. Although the results are reported in papers and reviews, it is sometimes difficult for those not themselves active in these fields to find their way through the mass of published material. We hope that each book in this series will present a clear account of the present state of knowledge in a particular field of physical chemistry to research workers in related fields, to research students, and for the preparation of undergraduate and post-graduate lectures. Each chapter describes the theoretical develop ment of one area of study and the appropriate experimental techniques; the results presented are chosen to illustrate the theory rather than to attempt a comprehensive review. The first volume published in 1972 was concerned with the reactions of small molecules and free radicals in the gas phase. The development of flash photolysis in the 1950s paved the way by making it possible to generate free radicals in sufficient concentration for a spectroscopic" snapshot" to reveal their molecular structure. Their role in kinetic systems could then be followed directly, rather than be inferred from mechanism. The shock tube enabled gas mixtures to be heated to any desired temperature in a time which was shorter than subsequent chemical reactions. Discharge-flow methods enabled the reactions of atoms and free radicals to be studied directly.




Unstable Chemical Species


Book Description




The Chemistry of Free Radicals


Book Description




Reactions of Ions with Atomic and Molecular Free Radicals. Progress Report, May 1, 1976--April 30, 1977. [0. 002 to 20 EV, Mechanisms, Adiabaticity].


Book Description

A program of research undertaken to study the dynamics of the reactions of ions with atomic and molecular free radicals. The objectives of this research are to obtain fundamental information on reaction mechanisms in reactions of species with open-shell electronic configurations, and to investigate the importance of electronic nonadiabaticity in chemical reactions. During the past contract year the systems D/sub 2//sup +/ + F .-->. FD/sup +/ + D and D/sub 2//sup +/ + C .-->. CD/sup +/ + D were studied over the range of initial kinetic energy from 0.002 eV to 20 eV. In both reactions the product ion is scattered preferentially in the direction of the incident atom. The FD/sup +/ product ion is formed in the ground /sup 2/PI state. The unusually large internal excitation energy of CD/sup +/, however, suggests that it is formed in an excited electronic state, possibly /sup 1/PI. The data for the D/sub 2//sup +/ + C reaction can be reconciled with the assumption of electronic adiabaticity, while that for D/sub 2//sup +/ + F probably cannot.




State Selected and State-to-State Ion-Molecule Reaction Dynamics, Volume 82, Part 1


Book Description

State-Selected and State-to-State Ion-Molecules Reaction Dynamics details the recent experimental and theoretical accomplishments in the field to date by some of its foremost researchers and theorists. Divided into two parts, each of which separately describe the experimental and theoretical aspects of the field, State-Selected and State-to-State Ion-Molecule Reaction Dynamics is an accessible, well organized look at a highly useful and emerging chemical specialty. Part 1, "Experiment," contains eight in-depth studies, which illustrate the key experimental work being done in the field today: Chapter 1 provide a comprehensive review of the theory and application of inhomogeneous rf fields for the study of the dynamics of low-energy ion-molecules processes Chapter 2 describes the application of multiphoton ionization (MPI) for the preparation of reactant ion states Chapter 3 reviews the application of MPI schemes for state specific cross-section measurements involving transition metal cations Chapter 4 describes the development of the threshold photoelectron secondary ion coincidence (TESICO) method Chapter 5 presents the conceptual and practical aspects of a multicoincidence technique Chapter 6 details the experimental results obtained using the photoionization and differential reactivity methods Chapter 7 reviews the several recent crossed beam studies of charge transfer and collision-induced dissociation systems involving atomic and molecular ions Chapter 8 is a survey of 15 years of high resolution crossed beam scattering of protons with atoms, diatoms, and poly-atomic molecules State-Selected and State-to-State Ion-Molecule Reaction Dynamics, Part 1: Experiment offers professionals a true state-of-the-science look at this fascinating and increasingly influential subject.