LEADER 04935nam 2200685Ia 450 001 9910141161203321 005 20230801221402.0 010 $a1-283-40125-8 010 $a9786613401250 010 $a1-118-16611-6 010 $a1-118-16609-4 035 $a(CKB)2670000000138109 035 $a(EBL)818508 035 $a(OCoLC)769342424 035 $a(SSID)ssj0000576120 035 $a(PQKBManifestationID)11965907 035 $a(PQKBTitleCode)TC0000576120 035 $a(PQKBWorkID)10553681 035 $a(PQKB)11084142 035 $a(MiAaPQ)EBC818508 035 $a(Au-PeEL)EBL818508 035 $a(CaPaEBR)ebr10523239 035 $a(CaONFJC)MIL340125 035 $a(EXLCZ)992670000000138109 100 $a20111007d2012 uy 0 101 0 $aeng 135 $aur|n|---||||| 181 $ctxt 182 $cc 183 $acr 200 00$aRate constant estimation for thermal reactions$b[electronic resource] $emethods and applications /$fedited by Herbert DaCosta, Maohong Fan 210 $aHoboken, N.J. $cWiley$dc2012 215 $a1 online resource (360 p.) 300 $aDescription based upon print version of record. 311 $a1-118-16612-4 311 $a0-470-58230-8 320 $aIncludes bibliographical references and index. 327 $aRate 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 Properties 327 $a1.5. 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 ?f 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 Hypersurfaces 327 $a2.3. 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 ?-Lactams 327 $a2.6.3. 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 KIE 327 $a3.6.6. Statistical Errors and Efficiency 330 $aProviding 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-preci 606 $aChemical kinetics$xEffect of temperature on$xMathematics 606 $aNumerical calculations 606 $aThermochemistry$xMathematics 615 0$aChemical kinetics$xEffect of temperature on$xMathematics. 615 0$aNumerical calculations. 615 0$aThermochemistry$xMathematics. 676 $a541/.36 686 $aSCI007000$2bisacsh 701 $aDaCosta$b Herbert$0909924 701 $aFan$b Maohong$0909925 801 0$bMiAaPQ 801 1$bMiAaPQ 801 2$bMiAaPQ 906 $aBOOK 912 $a9910141161203321 996 $aRate constant estimation for thermal reactions$92036486 997 $aUNINA