04935nam 2200685Ia 450 991014116120332120230801221402.01-283-40125-897866134012501-118-16611-61-118-16609-4(CKB)2670000000138109(EBL)818508(OCoLC)769342424(SSID)ssj0000576120(PQKBManifestationID)11965907(PQKBTitleCode)TC0000576120(PQKBWorkID)10553681(PQKB)11084142(MiAaPQ)EBC818508(Au-PeEL)EBL818508(CaPaEBR)ebr10523239(CaONFJC)MIL340125(EXLCZ)99267000000013810920111007d2012 uy 0engur|n|---|||||txtccrRate constant estimation for thermal reactions[electronic resource] methods and applications /edited by Herbert DaCosta, Maohong FanHoboken, N.J. Wileyc20121 online resource (360 p.)Description based upon print version of record.1-118-16612-4 0-470-58230-8 Includes bibliographical references and index.Rate Constant Calculation for Thermal Reactions: Methods and Applications; CONTENTS; PREFACE; CONTRIBUTORS; PART I: METHODS; 1. Overview of Thermochemistry and Its Application to Reaction Kinetics; 1.1. History of Thermochemistry; 1.2. Thermochemical Properties; 1.3. Consequences of Thermodynamic Laws to Chemical Kinetics; 1.4. How to Get Thermochemical Values?; 1.4.1. Measurement of Thermochemical Values; 1.4.2. Calculation of Thermochemical Values; 1.4.2.1. Quantum Chemical Calculations of Molecular Properties; 1.4.2.2. Calculation of Thermodynamic Functions from Molecular Properties1.5. Accuracy of Thermochemical Values1.5.1. Standard Enthalpies of Formation; 1.5.2. Active Thermochemical Tables; 1.6. Representation of Thermochemical Data for Use in Engineering Applications; 1.6.1. Representation in Tables; 1.6.2. Representation with Group Additivity Values; 1.6.3. Representation as Polynomials; 1.6.3.1. How to Change Δf H298K Without Recalculating NASA Polynomials; 1.7. Thermochemical Databases; 1.8. Conclusion; References; 2. Calculation of Kinetic Data Using Computational Methods; 2.1. Introduction; 2.2. Stationary Points and Potential Energy Hypersurfaces2.3. Calculation of Reaction and Activation Energies: Levels of Theory and Solvent Effects2.3.1. Hartree-Fock and Post-Hartree-Fock Methods; 2.3.2. Methods Based on Density Functional Theory; 2.3.3. Computational Treatment of Solvent Effects; 2.4. Estimate of Relative Free Energies: Standard States; 2.5. Theoretical Approximate Kinetic Constants and Treatment of Data; 2.6. Selected Examples; 2.6.1. Relative Reactivities of Phosphines in Aza-Wittig Reactions; 2.6.2. Origins of the Stereocontrol in the Staudinger Reaction Between Ketenes and Imines to Form β-Lactams2.6.3. Origins of the Stereocontrol in the Reaction Between Imines and Homophthalic Anhydride2.7. Conclusions and Outlook; References; 3. Quantum Instanton Evaluation of the Kinetic Isotope Effects and of the Temperature Dependence of the Rate Constant; 3.1. Introduction; 3.2. Arrhenius Equation, Transition State Theory, and the Wigner Tunneling Correction; 3.3. Quantum Instanton Approximation for the Rate Constant; 3.4. Kinetic Isotope Effects; 3.4.1. Transition State Theory Framework for KIE3.6.6. Statistical Errors and EfficiencyProviding an overview of the latest computational approaches to estimate rate constants for thermal reactions, this book addresses the theories behind various first-principle and approximation methods that have emerged in the last twenty years with validation examples. It presents in-depth applications of those theories to a wide range of basic and applied research areas. When doing modeling and simulation of chemical reactions (as in many other cases), one often has to compromise between higher-accuracy/higher-precision approaches (which are usually time-consuming) and approximate/lower-preciChemical kineticsEffect of temperature onMathematicsNumerical calculationsThermochemistryMathematicsChemical kineticsEffect of temperature onMathematics.Numerical calculations.ThermochemistryMathematics.541/.36SCI007000bisacshDaCosta Herbert909924Fan Maohong909925MiAaPQMiAaPQMiAaPQBOOK9910141161203321Rate constant estimation for thermal reactions2036486UNINA