Comprehensive Chemical Kinetics - 1st Edition - ISBN: 9780444508935, 9780080543444

Comprehensive Chemical Kinetics, Volume 39

1st Edition

Unimolecular Kinetics, Part 1. The Reaction Step

Editors: Nicholas Green
Hardcover ISBN: 9780444508935
eBook ISBN: 9780080543444
Imprint: Elsevier Science
Published Date: 21st November 2003
Page Count: 262
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Table of 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.).

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

  1. Experimental approaches

    3.1.Preparation by electronic excitation

    3.2.Overtone pumping
    3.3. Stimulated emission pumping
  2. 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
  3. 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
  4. 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
  5. Product state distributions
    7.1. General considerations
    7.2. Vibrational state distributions
    7.3. Rotational state distributions
  6. 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
  7. Outlook


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.

Key Features

. Presents considerable advances in the field made during the last decade. . Treats both the statistical as well as the fully quantum mechanical view.


For advanced students, researchers and professionals with an interest in chemical kinetics and working in industry, university and government institutions.


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© Elsevier Science 2003
Elsevier Science
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@qu: "I would recommend this text to anyone involved in research involving kinetics. For those of us studying complex reaction systems, this volume is a real eye-opener to the elegant work and sophisticated level of understanding that researchers have accomplished in looking at one of the simplest of all chemical reactions." @source: R.A. Henderson, University of Newcastle, Newscastle-upon-Tyne, UK, JOURNAL OF ORGANOMETALLIC CHEMISTRY, Vol. 689, 2004

About the Editors

Nicholas Green Editor

Affiliations and Expertise

King's College London, London, U.K.