Foreword |
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v | |
Preface |
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vii | |
Preface to the second edition |
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x | |
Part A The Definition of the Model |
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1 | (116) |
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Elementary Quantum Chemistry |
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3 | (16) |
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3 | (3) |
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The Variational Principle |
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6 | (2) |
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The Hartree-Fock Approximation |
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8 | (5) |
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The Restricted and Unrestricted Hartree-Fock Models |
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13 | (1) |
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14 | (5) |
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Electron Density and Hole Functions |
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19 | (10) |
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19 | (1) |
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20 | (4) |
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24 | (5) |
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25 | (2) |
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27 | (2) |
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The Electron Density as Basic Variable: Early Attempts |
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29 | (4) |
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29 | (1) |
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30 | (1) |
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Slater's Approximation of Hartree-Fock Exchange |
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31 | (2) |
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The Hohenberg-Kohn Theorems |
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33 | (8) |
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The First Hohenberg-Kohn Theorem: Proof of Existence |
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33 | (3) |
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The Second Hohenberg-Kohn Theorem: Variational Principle |
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36 | (1) |
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The Constrained-Search Approach |
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37 | (2) |
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Do We Know the Ground State Wave Function in Density Functional Theory? |
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39 | (1) |
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39 | (2) |
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41 | (24) |
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Orbitals and the Non-Interacting Reference System |
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41 | (2) |
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43 | (4) |
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47 | (18) |
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The Kohn-Sham Potential is Local |
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47 | (1) |
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The Exchange-Correlation Energy in the Kohn-Sham and Hartree-Fock Schemes |
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48 | (1) |
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Do the Kohn-Sham Orbitals Mean Anything? |
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49 | (1) |
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Is the Kohn-Sham Approach a Single Determinant Method? |
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50 | (2) |
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The Unrestricted Kohn-Sham Formalism |
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52 | (3) |
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On Degeneracy, Ensembles and other Oddities |
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55 | (4) |
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Excited States and the Multiplet Problem |
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59 | (6) |
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The Quest for Approximate Exchange-Correlation Functionals |
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65 | (28) |
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Is There a Systematic Strategy? |
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65 | (2) |
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67 | (2) |
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From Holes to Functionals |
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69 | (1) |
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The Local Density and Local Spin-Density Approximations |
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70 | (5) |
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The Generalized Gradient Approximation |
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75 | (3) |
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78 | (7) |
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85 | (3) |
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Asymptotic Behavior of Exchange-Correlation Potentials |
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88 | (1) |
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89 | (4) |
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The Basic Machinery of Density Functional Programs |
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93 | (24) |
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Introduction of a Basis: The LCAO Ansatz in the Kohn-Sham Equations |
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93 | (4) |
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97 | (5) |
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The Calculation of the Coulomb Term |
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102 | (3) |
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Numerical Quadrature Techniques to Handle the Exchange-Correlation Potential |
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105 | (5) |
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Grid-Free Techniques to Handle the Exchange-Correlation Potential |
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110 | (3) |
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Towards Linear Scaling Kohn-Sham Theory |
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113 | (4) |
Part B The Performance of the Model |
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117 | (148) |
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Molecular Structures and Vibrational Frequencies |
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119 | (18) |
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119 | (11) |
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Molecular Structures of Covalently Bound Main Group Elements |
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119 | (8) |
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Molecular Structures of Transition Metal Complexes |
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127 | (3) |
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130 | (7) |
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Vibrational Frequencies of Main Group Compounds |
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131 | (4) |
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Vibrational Frequencies of Transition Metal Complexes |
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135 | (2) |
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Relative Energies and Thermochemistry |
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137 | (40) |
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137 | (12) |
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149 | (8) |
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Bond Strengths in Transition Metal Complexes |
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157 | (6) |
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163 | (3) |
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166 | (2) |
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Electron Excitation Energies and the Singlet/Triplet Splitting in Carbenes |
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168 | (9) |
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177 | (20) |
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178 | (2) |
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180 | (3) |
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183 | (5) |
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188 | (3) |
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Infrared and Raman Intensities |
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191 | (6) |
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197 | (20) |
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198 | (3) |
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201 | (8) |
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NMR Nuclear Spin-Spin Coupling Constants |
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209 | (2) |
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211 | (1) |
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Hyperfine Coupling Constants |
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211 | (3) |
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214 | (3) |
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Hydrogen Bonds and Weakly Bound Systems |
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217 | (22) |
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The Water Dimer---A Worked Example |
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221 | (9) |
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230 | (2) |
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Other Hydrogen Bonded Systems |
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232 | (4) |
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The Dispersion Energy Problem |
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236 | (3) |
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Chemical Reactivity: Exploration of Potential Energy Surfaces |
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239 | (26) |
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First Example: Pericyclic Reactions |
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240 | (7) |
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Electrocyclic Ring Opening of Cyclobutene |
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241 | (2) |
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Cycloaddition of Ethylene to Butadiene |
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243 | (4) |
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Second Example: The SN2 Reaction at Saturated Carbon |
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247 | (2) |
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Third Example: Proton Transfer and Hydrogen Abstraction Reactions |
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249 | (6) |
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Proton Transfer in Malonaldehyde Enol |
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249 | (3) |
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A Hydrogen Abstraction Reaction |
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252 | (3) |
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Fourth Example: H2 Activation by FeO+ in the Gas Phase |
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255 | (10) |
Bibliography |
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265 | (30) |
Index |
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295 | |