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The present monograph appears after the death of Professor V. N.
Kondratiev, one of those scientists who have greatly contributed to
the foundation of contem porary gas kinetics. The most fundamental
idea of chemical kinetics, put for ward at the beginning of the
twentieth century and connected with names such as W. Nernst, M.
Bodenstein, N. N. Semenov, and C. N. Hinshelwood, was that the
complex chemical reactions are in fact a manifestation of a set of
simpler elementary reactions involving but a small number of
species. V. N. Kondratiev was one of the first to adopt this idea
and to start investigations on the elementary chemical reactions
proper. These investigations revealed explicitly that every
elementary reaction in turn consisted of many elementary events
usually referred to as elementary processes. It took some time to
realize that an elementary reaction, represented in a very simple
way by a macroscopic kinetic equation, can be described on a
microscopic level by a generalized Boltzmann equation. Neverheless,
up to the middle of the twentieth century, gas kinetics was mainly
concerned with the interpretation of complex chemical reactions via
a set of elementary reactions. But later on, the situation changed
drastically. First, the conditions for reducing microscopic
cquations to macroscopic ones were clearly set up. These are
essentially based on the fact that the small perturbations of the
Maxwell-Boltzmann distribution are caused by the reaction proper."
The theory of atom-molecule collisions is one of the basic fields
in chemi cal physics. Its most challenging part - the dynamics of
chemical reactions - is as yet unresolved, but is developing very
quickly. It is here a great help to have an analysis of those parts
of collision theory which are already complete, a good example
being the theory of atomic collisions in process es specific to
chemical physics. It has long been observed that many notions of
this theory can also be applied successfully to reactive and
unreactive molecular collisions. More over, atomic collisions often
represent a touchstone in testing approaches proposed for the
solution of more complicated problems. Research on the theory of
slow atomic collisions carried out at the Moscow Institute of
Chemical Physics has been based on just these ideas. A general
viewpoint concerning the setting up and representation of the
theory came out of these studies, and appeared to be useful in
studying complicated systems as well. It underlies the
representation of the theory of slow atomic colli sions in this
book."
Introduction 1 1. 2. Basic Concepts and Phenomenological
Description 6 2.1. Separation of the Center-of-Mass Motion 8 2.2.
Separation of Electronic and Nuclear Motions. Interaction
Potentials (Potential-Energy Surfaces) 11 2.2.1. Heuristic
Considerations 11 2.2.2. Born-Oppenheimer Separation. Adiabatic
Approximation, 16 Present State of Potential-Energy-Burface 2.2.3.
Calculations 23 2.3. Scattering Channels ~6 2.4. Classification of
Elementary Processes. Microscopic Mechanism 27 D.ynamics of Atomic
and Molecular Collisions: 3. Electronically Adiabatic Processes 32
Classical Approach 3.1. 33 Some Arguments for the Reliability of
the Classical Approach 33 Atom-Atom Collisions. Elastic Scattering
34 Quasiclassical Treatment of Elementary Processes in Triatomic
Systems: Inelastic and Reactive Scattering 44 IV Examples of
Results of Trajectory Calculations 59 3.1.4. 64 Elements of
Quantum-Mechanical Methods 3.2. Correspondence of Classical and
Quantum 3.2.1. 64 Mechanical Theories Time-Dependent Scattering
Theory 71 3.2.2. Stationary Scattering Theory 77 3.2.3.
One-Dimensional Scattering 78 3.2.3.1 * Three-Dimensional Elastic
Scattering 83 3.2.3.2. Rearrangement Scattering (Reactions) 85
3.2.3.3. Examples of Quantum-Mechanical Calculations 3.2.4.
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