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Reaction Rate Theory and Rare Events,

Edition 1

Editors: By Baron Peters

Publication Date: 22 Mar 2017

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Reaction Rate Theory and Rare Events bridges the historical gap between these subjects because the increasingly multidisciplinary nature of scientific research often requires an understanding of both reaction rate theory and the theory of other rare events. The book discusses collision theory, transition state theory, RRKM theory, catalysis, diffusion limited kinetics, mean first passage times, Kramers theory, Grote-Hynes theory, transition path theory, non-adiabatic reactions, electron transfer, and topics from reaction network analysis. It is an essential reference for students, professors and scientists who use reaction rate theory or the theory of rare events.

In addition, the book discusses transition state search algorithms, tunneling corrections, transmission coefficients, microkinetic models, kinetic Monte Carlo, transition path sampling, and importance sampling methods. The unified treatment in this book explains why chemical reactions and other rare events, while having many common theoretical foundations, often require very different computational modeling strategies.

Key Features

Offers an integrated approach to all simulation theories and reaction network analysis, a unique approach not found elsewhere
Gives algorithms in pseudocode for using molecular simulation and computational chemistry methods in studies of rare events
Uses graphics and explicit examples to explain concepts
Includes problem sets developed and tested in a course range from pen-and-paper theoretical problems, to computational exercises

About the author

By Baron Peters, Professor, Chemical Engineering Department, University of California at Santa Barbara, Santa Barbara, CA, USA

Chapter 1: Introduction

Abstract
1.1. Motivation for this book
1.2. Why are rare events important?
1.3. The role of computation and simulation
1.4. Polemics
References

Chapter 2: Chemical equilibrium

Abstract
2.1. Chemical potential and activity
2.2. Equilibrium constants and compositions
Exercises
References

Chapter 3: Rate laws

Abstract
3.1. Rates, mass balances, and reactors
3.2. Reaction order and elementary reactions
3.3. Initial rates and integrated rate laws
3.4. Reversible reactions
3.5. Multistep reactions
3.6. The pseudo-steady-state approximation
3.7. Rate determining steps and quasi-equilibrated steps
Exercises
References

Chapter 4: Catalysis

Abstract
4.1. Acid-base catalysis
4.2. Enzymes
4.3. Heterogeneous catalysis
4.4. Microkinetic models
4.5. Degree-of-rate-control
4.6. Catalysts with non-uniform sites
Exercises
References

Chapter 5: Diffusion control

Abstract
5.1. Complete diffusion control
5.2. Partial diffusion control
5.3. Diffusion control with long range interactions
5.4. Diffusion control for irregularly shaped reactants
Exercises
References

Chapter 6: Collision theory

Abstract
6.1. Hard spheres: Trautz and Lewis
6.2. Cross sections and rate constants
Exercises
References

Chapter 7: Potential energy surfaces and dynamics

Abstract
7.1. Molecular potential energy surfaces
7.2. Atom-exchange reactions
7.3. Mass weighted coordinates and normal modes
7.4. Features of molecular potential energy surfaces
7.5. Reaction path Hamiltonian
7.6. Empirical valence bond models
7.7. Disconnectivity graphs
Exercises
References

Chapter 8: Saddles on the energy landscape

Abstract
8.1. Newton-Raphson
8.2. Cerjan-Miller algorithm
8.3. Partitioned-Rational Function Optimization
8.4. The dimer method
8.5. Reduced landscape algorithms
8.6. Coordinate driving
8.7. Nudged elastic band
Exercises
References

Chapter 9: Unimolecular reactions

Abstract
9.1. Lindemann-Christiansen mechanism
9.2. Hinshelwood and RRK theories
9.3. RRKM theory
9.4. Transition state theory from RRKM theory
Exercises
References

Chapter 10: Transition state theory

Abstract
10.1. Foundations
10.2. Statistical mechanics for chemical equilibria
10.3. Harmonic transition state theory
10.4. Thermodynamic formulation
10.5. Flux across a dividing surface
10.6. Variational transition state theory
10.7. Harmonic TST with internal coordinates
10.8. Non-idealities
Exercises
References

Chapter 11: Landau free energies and restricted averages

Abstract
11.1. Monte Carlo, molecular dynamics, and hybrid sampling
11.2. Thermodynamic perturbation theory
11.3. Projections
11.4. Non-Boltzmann sampling
11.5. Thermodynamic integration
11.6. Other methods for computing free energies
11.7. Cautionary notes
Exercises
References

Chapter 12: Tunneling

Abstract
12.1. One-dimensional tunneling models
12.2. Kinetic isotope effects
12.3. Tunneling or tunnel splitting
12.4. Multidimensional tunneling models
Exercises
References

Chapter 13: Reactive flux

Abstract
13.1. Phenomenological rate laws and time correlations
13.2. Reactive flux formalism
13.3. Effective positive flux
13.4. Quantum dynamical correlation functions
Exercises
References

Chapter 14: Discrete stochastic variables

Abstract
14.1. Basic definitions
14.2. The master equation
14.3. Classical nucleation theory
14.4. Kinetic Monte Carlo
14.5. Markov state models
14.6. Spectral theory
Exercises
References

Chapter 15: Continuous stochastic variables

Abstract
15.1. Inertial Langevin dynamics
15.2. Overdamped Langevin dynamics
15.3. Fokker-Planck equations
15.4. From discrete models to Fokker-Planck equations
15.5. Stationary solutions of Fokker-Planck equations
15.6. Spectral theory revisited
Exercises
References

Chapter 16: Kramers theory

Abstract
16.1. Intermediate and high friction
16.2. Low friction: the energy diffusion limit
16.3. Insights and limitations
Exercises
References

Chapter 17: Grote-Hynes theory

Abstract
17.1. The Grote-Hynes equations
17.2. Multidimensional models and interpretations
Exercises
References

Chapter 18: Diffusion over barriers

Abstract
18.1. The forward and backward equations
18.2. Mean first passage times
18.3. Langer's multidimensional theory
18.4. Committors (splitting probabilities)
18.5. Berezhkovskii and Szabo: back to one dimension
18.6. Classical nucleation theory revisited
18.7. Rates from the committor
18.8. Discrete committors and rates
Exercises
References

Chapter 19: Transition path sampling

Abstract
19.1. The transition path ensemble
19.2. Transition path sampling
19.3. Basin definitions and foliations
19.4. Rate constants from transition path sampling
19.5. Transition interface sampling
19.6. Forward flux sampling
Exercises
References

Chapter 20: Reaction coordinates and mechanisms

Abstract
20.1. Properties of an ideal reaction coordinate
20.2. Variational theories and eigenfunctions
20.3. Committor analysis
20.4. Square error minimization
20.5. Likelihood maximization
20.6. Inertial likelihood maximization
Exercises
References

Chapter 21: Nonadiabatic reactions

Abstract
21.1. Diabatic and adiabatic representations
21.2. Spin-forbidden reactions
21.3. Electron transfer
21.4. Classical MD methods for electron transfer
21.5. Nonadiabatic models of enzyme catalysis
Exercises
References

Chapter 22: Free energy relationships

Abstract
22.1. BEP relations and the Bronsted catalysis law
22.2. The Marcus equation
22.3. Externally controlled driving forces
Exercises
References

ISBN: 9780444563491

Page Count: 634

Retail Price (USD) :

Frenkel and Smit, Understanding Molecular Simulation: From Algorithms to Applications, 2nd Edition, 9780122673511, AP, 664 pages, 2002, $91.95
Parmon, Thermodynamics of Non-Equilibrium Processes for Chemists with a Particular Application to Catalysis, 9780444530288, Elsevier, 340 pages, 2010, $255.00
Demirel, Nonequilibrium Thermodynamics: Transport and Rate Processes in Physical, Chemical and Biological Systems, 2nd Edition, 9780444530790, Elsevier, 754 pp, 2007, $245.00

Chemists, physicists, and engineers worldwide who use computational methods to study activated processes will be interested in this book. Academics, Graduate students, and Researchers in National Labs and corporate Research centers. The book could be used for teaching graduate courses

Reaction Rate Theory and Rare Events,

Editors: By Baron Peters

Key Features

About the author

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