Rate Constant Calculation for Thermal Reactions

Herbert DaCosta is currently a principal consultant at Chem-Innovations LLC and an adjunct professor of chemistry at Illinois Central College. His research interests include environmental catalysis and clean energy, nanomaterial design and synthesis, computational chemistry, and kinetics. Maohong Fan is Associate Professor at the University of Wyoming and an adjunct associate professor at the Georgia Institute of Technology. His research interests include nanomaterial synthesis and application, green processes for chemical production, and new approaches to clean energy generation.

• PREFACE xiiiHerbert DaCosta and Maohong Fan CONTRIBUTORS xvPART I METHODS 11. Overview of Thermochemistry and Its Application to Reaction Kinetics 3Elke Goos and Alexander Burcat1.1. History of Thermochemistry 31.2. Thermochemical Properties 51.3. Consequences of Thermodynamic Laws to Chemical Kinetics 81.4. How to Get Thermochemical Values? 101.5. Accuracy of Thermochemical Values 161.6. Representation of Thermochemical Data for Use in Engineering Applications 211.7. Thermochemical Databases 261.8. Conclusion 272. Calculation of Kinetic Data Using Computational Methods 33Fernando P. Cossío2.1. Introduction 332.2. Stationary Points and Potential Energy Hypersurfaces 342.3. Calculation of Reaction and Activation Energies: Levels of Theory and Solvent Effects 382.4. Estimate of Relative Free Energies: Standard States 472.5. Theoretical Approximate Kinetic Constants and Treatment of Data 502.6. Selected Examples 512.7. Conclusions and Outlook 613. Quantum Instanton Evaluation of the Kinetic Isotope Effects and of the Temperature Dependence of the Rate Constant 67Jiøí Vanícek3.1. Introduction 673.2. Arrhenius Equation, Transition State Theory, and the Wigner Tunneling Correction 683.3. Quantum Instanton Approximation for the Rate Constant 693.4. Kinetic Isotope Effects 713.5. Temperature Dependence of the Rate Constant 733.6. Path Integral Representation of Relevant Quantities 753.7. Examples 813.8. Summary 884. Activation Energies in Computational Chemistry—A Case Study 93Michael Busch, Elisabet Ahlberg and Itai Panas4.1. Introduction 934.2. Context and Theoretical Background 954.3. Computational Details 994.4. Recent Advances and New Results 994.5. Concluding Remarks 1075. No Barrier Theory—A New Approach to Calculating Rate Constants in Solution 113J. Peter Guthrie5.1. Introduction 1135.2. The Idea Behind No Barrier Theory 1145.3. How to Define the Surface and Find the Transition State 1185.4. What is Needed for a Calculation? 1245.5. Applications to Date 1255.6. Future Prospects for NBT 140PART II MINIREVIEWS AND APPLICATIONS 1476. Quantum Chemical and Rate Constant Calculations of Thermal Isomerizations, Decompositions, and Ring Expansions of Organic Ring Compounds, Its Significance to Cohbusion Kinetics 149Faina Dubnikova and Assa Lifshitz6.1. Prologue 1496.2. Small Organic Ring Compounds 1526.3. Pyrrole and Indole 1566.4. Dihydrofurans and Dihydrobenzofurans 1606.5. Naphthyl Acetylene–Naphthyl Ethylene 1666.6. Ring Expansion Processes 1686.7. Benzoxazole–Benzisoxazoles 1736.8. Conclusion 1817. Challenges in the Computation of Rate Constants for Lignin Model Compounds 191Ariana Beste and A.C. Buchanan, III7.1. Lignin: A Renewable Source of Fuels and Chemicals 1917.2. Mechanistic Study of Lignin Model Compounds 1967.3. Computational Investigation of the Pyrolysis of β-O-4 Model Compounds 2017.4. Case Studies: Substituent Effects on Reactions of Phenethyl Phenyl Ethers 2147.5. Conclusions and Outlook 2328. Quantum Chemistry Study on the Pyrolysis Mechanisms of Coal-Related Model Compounds 239Baojun Wang, Riguang Zhang and Lixia Ling8.1. Introduction to the Application of Quantum Chemistry Calculation to Investigation on Models of Coal Structure 2398.2. The Model for Coal Structure and Calculation Methods 2408.3. The Pyrolysis Mechanisms of Coal-Related Model Compounds 2438.4. Conclusion 2769. Ab Initio Kinetic Modeling of Free-Radical Polymerization 283Michelle L. Coote9.1. Introduction 2839.2. Ab Initio Kinetic Modeling 2879.3. Quantum Chemical Methodology 2919.4. Case Study: RAFT Polymerization 2969.5. Outlook 30010. Intermolecular Electron Transfer Reactivity for Organic Compounds Studied Using Marcus Cross-Rate Theory 305Stephen F. Nelsen and Jack R. Pladziewicz10.1. Introduction 30510.2. Determination of ∆G‡ii (fit) Values 30710.3. Why is the Success of Cross-Rate Theory Surprising? 30910.4. Major Factors Determining Intrinsic Reactivities of Hydrazine Couples 31010.5. Nonhydrazine Couples 31510.6. Comparison of D∆G‡ii (fit) with D∆G‡ii (self) Values 31810.7. Estimation of Hab from Experimental Exchange Rate Constants and DFT-Computed l 32010.8. Comparison with Gas-Phase Reactions 33310.9. Conclusions 333References 334INDEX 337

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