Computational Chemistry Workbook
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1 Computational Chemistry Workbook Learning Through Examples Bearbeitet von Thomas Heine, Jan-Ole Joswig, Achim Gelessus 1. Auflage Taschenbuch. XVI, 234 S. Paperback ISBN Format (B x L): 17 x 24 cm Gewicht: 530 g Weitere Fachgebiete > Chemie, Biowissenschaften, Agrarwissenschaften > Physikalische Chemie > Quantenchemie, Theoretische Chemie Zu Leseprobe schnell und portofrei erhältlich bei Die Online-Fachbuchhandlung beck-shop.de ist spezialisiert auf Fachbücher, insbesondere Recht, Steuern und Wirtschaft. Im Sortiment finden Sie alle Medien (Bücher, Zeitschriften, CDs, ebooks, etc.) aller Verlage. Ergänzt wird das Programm durch Services wie Neuerscheinungsdienst oder Zusammenstellungen von Büchern zu Sonderpreisen. Der Shop führt mehr als 8 Millionen Produkte.
2 XI Foreword VII Acknowledgments IX 1 Introduction Basics of Computational Chemistry Aim of This Book How to Use This Book Structure of This Book The Chapters The Software 9 2 Molecular Coordinates and Symmetry Aim Theoretical Background Cartesian and Internal Coordinates The Z-Matrix The Dihedral Angle Symmetry Symmetry Elements and Operations Point Groups Demonstration Constructing a Z-Matrix Determining Molecular Point Groups Problems Technical Details Review and Summary 23 References 23 Computational Chemistry Workbook: Learning Through Examples Thomas Heine, Jan-Ole Joswig, and Achim Gelessus Copyright Ó 2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim ISBN:
3 XII 3 Vibrations of Diatomic Molecules: The Harmonic Approximation Aim Theoretical Background The Harmonic Approximation The Reduced Mass The Vibrational Frequencies Demonstration Problems Technical Details Review and Summary 34 References 34 4 Vibrations of Diatomic Molecules: The Schrödinger Equation Aim Theoretical Background Classical Versus Quantum Mechanics The Stationary Schrödinger Equation Solutions to the Schrödinger Equation Demonstration Problems Technical Details Review and Summary 45 References 45 5 Atomic Orbitals Aim Theoretical Background The Schrödinger Equation of the Atom Atomic Orbitals Demonstration Problems Technical Details Review and Summary 54 References 55 6 Ionization Potentials and Electron Affinities of Atoms Aim Theoretical Background Ionization Potential and Electron Affinity Slater Rules: Wavefunction and Binding Energies of Electrons in Atoms and Ions Calculation of Ionization Potentials and Electron Affinities 61
4 XIII 6.3 Demonstration Problems Technical Details Review and Summary 66 References 66 7 Hückel Molecular Orbital Theory: Stability of Conjugated Carbon p Systems Aim Theoretical Background Molecular Orbital Theory The Hückel Postulates Topology Matrices Values for a and b The Trap of Defining x p Electron Binding Energy p Electron Molecular Orbitals and Probability Density Demonstration Hückel Calculation of the Cyclopropenyl Cation Problems Technical Details Review and Summary 80 References 81 8 Hückel Molecular Orbital Theory: Bond Order, Charge Order, and Molecular Orbitals Aim Theoretical Background Bond Order Charge Order Demonstration Hückel Calculation of the Butadiene Molecule Problems Review and Summary 89 References 90 9 Geometry Optimization of a Diatomic Molecule Aim Theoretical Background The Potential Energy Surface Forces in a Diatomic Molecule The Steepest Descent Method Hessian-Based Optimizers and the Newton Raphson Method Application to the Morse Potential 97
5 XIV Global Versus Local Geometry Optimization Demonstration Optimizing CO With the Steepest Descent Method Optimizing CO Using a Hessian-Based Newton Raphson Optimizer Problems Technical Details Review and Summary 104 References The Electron Spin Aim Theoretical Background The Electron Spin The Multiplicity The Jahn Teller Effect Demonstration Problems Technical Details Review and Summary 112 References Vibrational Spectroscopy Aim Theoretical Background Analysis of Classical Vibrations Within the Harmonic Approximation The Harmonic Oscillator Revisited The Vibrational Modes Intensities Demonstration The Vibrational Modes of a Linear Molecule Problems Technical Details Review and Summary 126 References Vibrational Spectroscopy and Character Tables Advanced Topics Aim Theoretical Background The Hessian Matrix Normal Modes Symmetry in Normal Modes 130
6 XV Selection Rules Demonstration Problems Review and Summary 140 References Ionization Potential and Electron Affinities of Molecules Aim Theoretical Background Field of Application Influence of Geometry Demonstration Problems Technical Details Review and Summary 148 References Thermochemistry Aim Theoretical Background Calculating Thermodynamic Functions Using the Partition Function Thermochemistry Within the Ideal-Gas Approximation The Molecular Partition Function q Calculating the Relative Abundance of Isomers in the Gas Phase Demonstration Problems Review and Summary 165 References Molecular Dynamics Basic Concepts Aim Theoretical Background Computer Simulations in Chemistry The Born Oppenheimer Approximation The Trajectory: Startup Conditions and Propagation of Atoms in Time The Verlet Algorithm The Velocity Verlet Algorithm Conservation of Fundamental Physical Quantities: Energy, Momentum, and Angular Momentum Numerical Considerations 173
7 XVI Heat Bath: Thermostats Demonstration Classical Molecular Dynamics in a Spreadsheet Problems Review and Summary 178 References Molecular Dynamics and Basic Thermodynamics Aim Theoretical Background Basic Thermodynamics: Ensembles The Temperature and the Ergodic Theorem The Connection to Real Macroscopic Systems External Heat Baths Thermostats A Simple Scaling Thermostat The Berendsen Thermostat The Andersen Thermostat The Nosé-Hoover Thermostat Averages Demonstration Problems Review and Summary 195 References Molecular Dynamics Simulated Annealing Aim Theoretical Background The Potential Energy Surface Simulated Annealing Demonstration Inspecting Stationary Points With Simulated Annealing Finding the Global Minimum of Al 2 4 Using Simulated Annealing Problems Review and Summary 206 References 207 Appendix The Computational Chemistry Software Delivered with This Book 209 A.1 Getting Started 210 A.1.1 Booting Directly the Live System 210 A.1.2 Booting as Virtual Machine 210 A.1.3 Running From a Pen Drive (USB Stick) 211
8 XVII A.1.4 Configure Your Environment 213 A.2 A Brief Introduction to Linux 214 A.3 Character Tables for Chemically Important Point Groups 218 A.4 Computational Chemistry Software Delivered With This Book 219 A.4.1 Molden 219 A.4.2 demon 219 A.4.3 CaGe 220 A.4.4 hueckel 222 A.4.5 THERMO Scripts 222 A.4.6 Xmgrace 223 A.4.7 GNUplot 223 Index 225
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