List of Contributors |
Preface |
Introduction / Robert W. Carr1: |
Obtaining Molecular Thermochemistry from Calculations / Karl K. Irikura2: |
Introduction and overview |
Molecular mechanics |
Semiempirical molecular orbital theory / 3: |
Molecular orbital theory / 4: |
Physical approximations / 4.1: |
Numerical approximations / 4.2: |
Density functional theory / 5: |
Theory and basis set: examples / 6: |
Electron affinity of fluorine / 6.1: |
Bond dissociation energy in methane / 6.2: |
Proton affinity of ammonia / 6.3: |
Excitation energy of singlet O[subscript 2] / 6.4: |
Thermochemistry from ab initio calculations / 7: |
Temperatures besides 298.15 K / 7.1: |
Recognizing trouble, ab initio / 8: |
Summary / 9: |
References |
Elements of Chemical Kinetics |
Elementary concepts |
Stoichiometry / 2.1: |
The reaction rate / 2.2: |
The rate expression / 2.3: |
Elementary reactions / 2.4: |
State-to-state kinetics / 2.5: |
The temperature dependence of the rate coefficient / 2.6: |
Kinetic data / 2.7: |
Mechanism / 2.8: |
The steady state approximation / 2.9: |
Microscopic reversibility and detailed balance / 2.10: |
Potential energy |
The Born-Oppenheimer approximation / 3.1: |
Long-range potentials / 3.2: |
Short-range repulsive forces / 3.3: |
Bonding interactions / 3.4: |
Potential energy surfaces / 3.5: |
Bimolecular reaction rate theory |
Simple collision theory |
Bimolecular collision dynamics |
Ion-molecule reactions / 4.3: |
Ion-ion reactions / 4.4: |
Bimolecular association of free radicals / 4.5: |
Classical trajectory calculations / 4.6: |
Transition state theory / 4.7: |
The statistical factor / 4.8: |
Tests of transition state theory / 4.9: |
Microcanonical transition state theory / 4.10: |
Variational transition state theory / 4.11: |
The transmission coefficient / 4.12: |
Tunneling / 4.13: |
Electronically non-adiabatic reactions / 4.14: |
Termolecular Reactions |
The Kinetics of Pressure-Dependent Reactions / Hans-Heinrich Carstensen ; Anthony M. Dean |
Review of pressure-dependent reactions |
Unimolecular reactions |
Chemically activated reactions |
Energy transfer models |
The master equation approach for single-well systems |
Complex pressure-dependent systems |
Practical methods to analyze pressure-dependent reactions |
Software for the calculation of pressure-dependent rate constants |
Getting input data for the calculations |
Worked-out examples of the analysis of pressure-dependent reactions |
Example 1: the thermal dissociation C[subscript 2]H[subscript 5]O[right arrow]CH[subscript 3]+CH[subscript 2]O |
Example 2: the isomerization reaction n-C[subscript 3]H[subscript 7] [Characters not reproducible] i-C[subscript 3]H[subscript 7] |
Example 3: the reaction C[subscript 2]H[subscript 5]+O[subscript 2 right arrow]products |
Example 4: the reaction C[subscript 2]H[subscript 3]+O[subscript 2] products |
Representation of k(T, p) rate coefficients for modeling |
Single-well single-channel systems / 5.1: |
Multi-well multi-channel systems / 5.2: |
Summary and look to the future |
Constructing Reaction Mechanisms / Mark T. Swihart |
Identifying reactions |
Finding reactions and reaction mechanisms in the literature |
Identifying reactions by analogy |
Identifying reactions based on "chemical intuition,' or just making it up |
Determining species thermochemical properties |
Finding thermochemical properties in the literature |
Estimating thermochemical properties using group additivity |
Estimating thermochemical properties using computational quantum chemistry |
Estimating thermochemical properties by analogy or educated guessing |
Determining rate parameters |
Finding rate parameters in the literature |
Determining rate parameters using quantum chemical calculations and transition state theory |
Purely empirical estimation of rate parameters |
Linear free energy relationships and correlations for estimating activation energies |
Applying the mechanism at conditions of interest |
Reaction rate/flux analysis and sensitivity analysis |
Summary and outlook |
Optimization of Reaction Models With Solution Mapping / Michael Frenklach ; Andrew Packard ; Ryan Feeley |
Preliminary material and terminology |
Training data |
Objective function |
Optimization methods |
Parameter uncertainty |
Pitfalls of poor uncertainty management |
Statement of the problem |
Parameter estimation of dynamic models with solution mapping |
Solution mapping approach |
Effect sparsity and active variables |
Screening sensitivity analysis / 5.3: |
Factorial designs / 5.4: |
Optimization / 5.5: |
Prior pruning of the reaction model / 5.6: |
Strengths and weaknesses of solution mapping / 5.7: |
Data collaboration |
Data collaboration concepts |
Looking at some feasible sets from GRI-Mech dataset |
Optimization techniques primer |
Prediction of model uncertainty |
Consistency of a reaction dataset / 6.5: |
Information gain due to data collaboration / 6.6: |
Concluding remarks |
Acknowledgments |
Subject Index |
List of Contributors |
Preface |
Introduction / Robert W. Carr1: |