1 An Outline of What Computational Chemistry Is AII About 1.1 What You Can Do with Computational Chemistry 1.2 The Tools of Computational Chemistry 1.3 Putting lt All Together 1.4 The Philosophy of Computational Chemistry 1.5 Summary References Easier Questions Harder Questions 2 The Concept of the PotentiaI Energy Surface 2.1 Perspective 2.2 Stationary Points 2.3 The Born-Oppenheimer Approximation 2.4 Geometry Optimization 2.5 Stationary Points and Normal-Mode Vibrations-Zero Point Energy 2.6 Symmetry 2.7 Summary References Easier Questions Harder Questions 3 Molecular Mechanics 3.1 Perspective 3.2 The Basic Principles of Molecular Mechanics 3.2.1 Developing a Forcefield 3.2.2 Parameterizing a Forcefield 3.2.3 A Calculation Using Our Forcefield 3.3 Examples of the Use of Molecular Mechaoics 3.3.1 To Obtain Reasonable Input Geometries for Lengthier(Ab Initio,Serniempirical or Density Functional)Kinds of Calculations 3.3.2 To Obtaio Good Geometries(and Perhaps Energies)for Small-to Medium-Sized Molecules 3.3.3 To Calculate the Geometries and Energies of Very Large MoleculesUsuaUy Polymeric Biomolecules(Proteins and Nucleic Acids) 3.3.4 To Generate the Potential Energy Function Under Which Molecules Movefor Molecular Dynamics or Monte Carlo Calculations 3.3.5 As a(Usually Quick)Guide to the Feasibility of,or Likely Outcome of,Reactions in Organic Synthesis 3.4 Geometries Calculated by MM 3.5 Frequencies and Vibrational Spectra Calculated by MM 3.6 Strengths and Wealmesses of Molecular Mechanics 3.6.1 Strengths 3.6.2 Weaknesses 3.7 Summary References Easier Questions Harder Questions 4 Introduction to Quantum Mechanics in Computational Chemistry 4.1 Perspective 4.2 The Development of Quantum Mechanics.The Schrödinger Equation 4.2.1 The Origins of Quantum Theory:Blackbody Radiation and the Photoelectric Effect 4.2.2 Radioactivity 4.2.3 Relativity 4.2.4 The Nuclear Atom 4.2.5 The Bohr Atom 4.2.6 The Wave Mechanical Atom and the Schrödinger Equation 4.3 The Application of the Schrödinger Equation to Chernistry by Hückel 4.3.1 Introduction 4.3.2 Hybridization 4.3.3 Matrices and Determinants 4.3.4 The Simple Hückel Method-Theory 4.3.5 The Simple Hückel Method-Applications 4.3.6 Strengths and Weaknesses of the Simple Hückel Method 4.3.7 The Determinant Method of Calculating the Hückelc’s and Energy Levels 4.4 The Extended Hückel Method 4.4.1 Theory 4.4.2 An Il1ustration of the EHM:the Protonated Helium Molecule 4.4.3 The Extended Hückel Method-Applications 4.4.4 Strengths and Weaknesses of the Extended Hückel Method 4.5 Surnmary References Easier Questions Harder Questions 5 Ab initio Calculations 5.1 Perspective 5.2 The Basic Principles of the Ab initio Method 5.2.1 Preliminaries 5.2.2 The Hartree SCF Method 5.2.3 The Hartre Fock Equations 5.3 Basis Sets 5.3.1 Introduction 5.3.2 Gaussian Functions;Basis Set Preliminaries;Direct SCF 5.3.3 Types of Basis Sets and Their Uses 5.4 Post-Hatree-Fock Ca1culations:Electron Correlation 5.4.1 Electron Correlation 5.4.2 The Møller-Plesset Approach to Electron Correlation 5.4.3 The Configuration Interaction Approach To Electron Correlation-The Coupled Cluster Method 5.5 Applications of the Ab initio Method 5.5.1 Geometries 5.5.2 Energies 5.5.3 Frequencies and Vibrational Spectra 5.5.4 Properties Arising from Electron Distribution: Dipole MomentsChargesBond OrdersElectrostatic PotentialsAtoms-in-Molecules(AIM) 5.5.5 Miscellaneous Properties-UV and NMR SpectraIonizationEnergiesand Electron Afl:tities 5.5.6 Visualization 5.6 Strengths and Weaknesses of Ab initio Calculations 5.6.1 Strengths 5.6.2 Weaknesses 5.7 Surnmary References Easier Questions Harder Questions 6 Semiempirical Calculations 6.1 Perspective 6.2 The Basic Principles of SCF Semiempirical Methods 6.2.1 Preliminaries 6.2.2 The Pariser-Parr-Pople(PPP)Method 6.2.3 The Complete Neglect of Differential Overlap(CNDO)Method 6.2.4 The Intermediate Neglect of Differential Overlap(INDO)Method 6.2.5 The Neglect of Diatomic Differential Overlap(NDDO)Methods 6.3 Applications of Semiempirical Methods 6.3.1 Geometries 6.3.2 Energies 6.3.3 Frequencies and Vibrational Spectra 6.3.4 Properties Arising from Electron Distribution:Dipole Moments,Charges Bond Orders 6.3.5 Miscellaneous Properties-UV Spectra,Ionization Energies,and Electron Affinities 6.3.6 Visualization 6.3.7 Some General Remarks 6.4 Strengths and Weaknesses of Semiempirical Methods 6.4.1 Strengths 6.4.2 Weaknesses 6.5 Summary References Easier Questions Harder Questions 7 Density Functional Calculations 7.1 Perspective 7.2 The Basic Principles of Density Functional Theory 7.2.1 Preliminaries 7.2.2 Forerunners to Current DFT Methods 7.2.3 Current DFT Methods:The Kohn-Sham Approach 7.3 Applications of Density Functional Theory 7.3.1 Geometries 7.3.2 Energies 7.3.3 Frequencies aod Vibrational Spectra 7.3.4 Properties Arising from Electron Distribution-Dipole MomeotCs hargeBs ond OrderAs toms-in-Molecules 7.3.5 Miscellaneous Properties-UV and NMR Spectra Ionization Energies and Electron Affin ities EIctronegativity,Hardnesss oftness and the Fukui Function 7.3.6 Visualization 7.4 Strengths and Weaknesses of DFT 7.4.1 Strengths 7.4.2 Weaknesses 7.5 Summary References Easier Questions Harder Questions 8 Some“Special“Topics:Solvation,Singlet Diradicals,A Note on Heavy Atoms and Transition Metals 8.1 Solvation 8.1.1 Perspective 8.1.2 Ways of Treating Solvation 8.2 Singlet Diradicals 8.2.1 Perspective 8.2.2 Problems with Sing1et Diraclicals and Model Chemistries 8.2.3 (1)Singlet Diradicals: Beyond Model Chemistries(2)Complete Active Space Ca1culations(CAS) 8.3 A Note on Heavy Atoms and Transition Metals 8.3.1 Perspective 8.3.2 Heavy Atoms and Relativistic Corrections 8.3.3 Some Heavy Atom Calculations 8.3.4 Transition Metals 8.4 Summary References Solvation Easier Questions Harder Questions Singlet Diradicals Easier Questions Harder Questions Heavy Atoms and Transition Metals Easier Questions Harder Questions 9 Selected Literature Higbligbts,Books,Websites,Software and Hardware 9.1 From the Literature 9.1.1 Molecules 9.1.2 Mechanisms 9.1.3 Concepts 9.2 To the Literature 9.2.1 Books 9.2.2 Websites for Computational Chemistry in General 9.3 Software and Hardware 9.3.1 Software 9.3.2 Hardware 9.3.3 Postscript References Answers Index
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