Description Unimolecular reactions are in principle the simplest chemical reactions, because they only involve one molecule. The basic mechanism,
in which the competition between the chemical reaction step and a collisional deactivation leads to a pressure-dependent coefficient,
has been understood for a long time. However, this is a rapidly developing field, and many new and important discoveries have been made
in the past decade.
This First Part Part of Two CCK Volumes dealing with Unimolecular Rections, deals with the Reaction Step. The first
chapter is an introduction to the whole project, aiming to cover the material necessary to understand the content of the detailed chapters,
as well as the history of the development of the area. Chapter 2 is a review of the modern view of the statistical theories, as embodied
in the various forms of RRKM theory. Chapter 3 deals with the fully quantum mechanical view of reactive states as resonances.
Audience
For advanced students, researchers and professionals with an interest in chemical kinetics and working in industry, university and government institutions.
Contents
Chapter 1. Introduction
1. Introduction
2. Failures of the Lindemann Theory
2.1 Lindemann-Hinshelwood
theory
2.2 Curved Lindemann plot
3. RKK Theory
3.1. Classical RKK theory
3.2. Quantum RKK theory
3.3. Development
of the RKK theories
4. Slater Theory
5. RKKM theory
5.1. Classical RKKM theory
5.1.1. Phase space
5.1.2. The
density of states
5.1.3. Rate of flow through the transition state
5.1.4. RKKM rate coefficient
5.2. Improvements to RKKM
theory
5.2.1. Fixed and non-fixed energy
5.2.2. Angular momentum conservation
5.2.3. Statistical factor
5.2.4. Variational
methods
5.2.5. Density of states
5.2.6. Quantum effects
6. Statistical adiabatic channel model
7. Improved models
of energy transfer
7.1 Troe parametrizations
7.1.1 Low pressure limit
7.1.2 Parametrization of the fall-off
7.2 Master
equation
Chapter 2. RRKM Theory and Its Implementation(S.J. Klippenstein).
2.1. Background
2.2. Derivation of RRKM theory
2.2.1. Classical RRKM theory
2.3. Reactions with barriers
2.3.1. Conventional RRKM theory with Eckart tunneling
2.3.2.
The reaction path: variational effects and tunneling
2.3.3. Extensions of RRKM theory
2.4. Vibrational anharmonicities and
non-rigidi
2.4.1. Background
2.4.2. Internal rotors
2.4.3. Other separable modes
2.4.4. Full treatments
2.5.
Barrierless reactions
2.5.1. Background
2.5.2. Phase space theory, flexible RRKM theory, and the statistical adiabatic channel
model
2.5.3. Variable reaction coordinate RRKM theory
2.5.4. Potential energy surfaces in variable reaction coordinate RRKM
theory
2.5.5. Extensions of variable reaction coordinate RRKM theory
Chapter 3 State-specific dynamics of unimolecular
dissociation
S.Yu. Grebenshchikov et al.).
1.Introduction
2.Resonance formulation of unimolecular decay
2.1.One-dimensional square-well model
2.2. Multi-dimensional cases
2.3.Mixing between resonances: a simple model
3. Experimental
approaches
3.1.Preparation by electronic excitation
3.2.Overtone pumping
3.3. Stimulated emission pumping
4. Computational
methods
4.1. Overview
4.1.1. Indirect approaches
4.1.2. Direct approaches
4.1.3. Basis sets
4.2. Indirect approach:
Kohn variational principle
4.3. Direct approach: filter diagonalization with absorbing potential
5. Mode-specific dissociation
5.1. Dissociation of HCO
5.2. Dissociation of HOCl
5.3. Mixing between resonances tuned by rotational excitation
5.4. Epilogue
6. Statistical state-specific dissociation
6.1. Dissociation of H2CO and D2CO
6.2. Dissociation of NO2
6.3. Distribution of dissociation rates
6.4. "Steps" predicted by RRKM theory
7. Product state distributions
7.1. General
considerations
7.2. Vibrational state distributions
7.3. Rotational state distributions
8. Classical calculations
8.1. Classical dynamics of a micro-canonical ensemble: intrinsic RRKM and non-RKKM behavior
8.2. Phase-space structures
8.2.1.
Quasi-periodic and chaotic motions
8.2.2. Transition from quasi-periodic to chaotic motion
8.2.3. Models for non-ergodic dynamics
8.3 Simulations of molecular systems with non-random excitation
8.4. Direct dynamics simulations
8.5. Expected accuracy
of classical calculations
8.5.1. Decomposition of a micro-canonical ensemble -small molecules
8.5.2. Non-random excitation
- large molecules
9. Outlook
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