List of Contributors p. xiii
Preface p. xv
Introduction p. 1
Obtaining Molecular Thermochemistry from Calculations p. 7
Introduction and overview p. 7
Molecular mechanics p. 9
Semiempirical molecular orbital theory p. 12
Molecular orbital theory p. 14
Physical approximations p. 14
Numerical approximations p. 19
Density functional theory p. 22
Theory and basis set: examples p. 23
Electron affinity of fluorine p. 23
Bond dissociation energy in methane p. 24
Proton affinity of ammonia p. 25
Excitation energy of singlet O[subscript 2] p. 25
Thermochemistry from ab initio calculations p. 27
Temperatures besides 298.15 K p. 34
Recognizing trouble, ab initio p. 35
Summary p. 37
References p. 38
Elements of Chemical Kinetics p. 43
Introduction p. 43
Elementary concepts p. 43
Stoichiometry p. 43
The reaction rate p. 45
The rate expression p. 46
Elementary reactions p. 48
State-to-state kinetics p. 49
The temperature dependence of the rate coefficient p. 51
Kinetic data p. 54
Mechanism p. 55
The steady state approximation p. 58
Microscopic reversibility and detailed balance p. 60
Potential energy p. 64
The Born-Oppenheimer approximation p. 64
Long-range potentials p. 65
Short-range repulsive forces p. 65
Bonding interactions p. 66
Potential energy surfaces p. 67
Bimolecular reaction rate theory p. 72
Simple collision theory p. 72
Bimolecular collision dynamics p. 76
Ion-molecule reactions p. 77
Ion-ion reactions p. 78
Bimolecular association of free radicals p. 79
Classical trajectory calculations p. 80
Transition state theory p. 83
The statistical factor p. 85
Tests of transition state theory p. 86
Microcanonical transition state theory p. 88
Variational transition state theory p. 88
The transmission coefficient p. 90
Tunneling p. 90
Electronically non-adiabatic reactions p. 92
Termolecular Reactions p. 95
References p. 97
The Kinetics of Pressure-Dependent Reactions p. 101
Introduction p. 101
Review of pressure-dependent reactions p. 102
Unimolecular reactions p. 102
Chemically activated reactions p. 110
Energy transfer models p. 113
The master equation approach for single-well systems p. 118
Complex pressure-dependent systems p. 121
Practical methods to analyze pressure-dependent reactions p. 136
Software for the calculation of pressure-dependent rate constants p. 136
Getting input data for the calculations p. 137
Worked-out examples of the analysis of pressure-dependent reactions p. 157
Example 1: the thermal dissociation C[subscript 2]H[subscript 5]O[right arrow]CH[subscript 3]+CH[subscript 2]O p. 157
Example 2: the isomerization reaction n-C[subscript 3]H[subscript 7] [Characters not reproducible] i-C[subscript 3]H[subscript 7] p. 164
Example 3: the reaction C[subscript 2]H[subscript 5]+O[subscript 2 right arrow]products p. 167
Example 4: the reaction C[subscript 2]H[subscript 3]+O[subscript 2] products p. 172
Representation of k(T, p) rate coefficients for modeling p. 175
Single-well single-channel systems p. 175
Multi-well multi-channel systems p. 176
Summary and look to the future p. 178
References p. 180
Constructing Reaction Mechanisms p. 185
Introduction p. 185
Identifying reactions p. 188
Finding reactions and reaction mechanisms in the literature p. 188
Identifying reactions by analogy p. 192
Identifying reactions based on "chemical intuition,' or just making it up p. 194
Determining species thermochemical properties p. 198
Finding thermochemical properties in the literature p. 199
Estimating thermochemical properties using group additivity p. 202
Estimating thermochemical properties using computational quantum chemistry p. 203
Estimating thermochemical properties by analogy or educated guessing p. 203
Determining rate parameters p. 208
Finding rate parameters in the literature p. 209
Determining rate parameters using quantum chemical calculations and transition state theory p. 210
Purely empirical estimation of rate parameters p. 217
Linear free energy relationships and correlations for estimating activation energies p. 221
Applying the mechanism at conditions of interest p. 221
Reaction rate/flux analysis and sensitivity analysis p. 232
Summary and outlook p. 239
References p. 240
Optimization of Reaction Models With Solution Mapping p. 243
Introduction p. 243
Preliminary material and terminology p. 244
Training data p. 244
Objective function p. 245
Optimization methods p. 246
Parameter uncertainty p. 247
Pitfalls of poor uncertainty management p. 250
Statement of the problem p. 255
Parameter estimation of dynamic models with solution mapping p. 256
Solution mapping approach p. 256
Effect sparsity and active variables p. 258
Screening sensitivity analysis p. 258
Factorial designs p. 261
Optimization p. 268
Prior pruning of the reaction model p. 268
Strengths and weaknesses of solution mapping p. 271
Data collaboration p. 275
Data collaboration concepts p. 276
Looking at some feasible sets from GRI-Mech dataset p. 277
Optimization techniques primer p. 279
Prediction of model uncertainty p. 282
Consistency of a reaction dataset p. 283
Information gain due to data collaboration p. 285
Concluding remarks p. 288
Acknowledgments p. 289
References p. 289
Subject Index p. 293