Molecular Electrostatic Potentials (eBook)

Front Cover 1
Molecular Electrostatic Potentials: Concepts and Applications 4
Copyright Page 5
Table of Contents 8
Chapter 1. MEP: A Tool for Interpretation and Prediction. From Molecular Structure to Solvation Effects 16
1. Introduction 16
2. Thirty Years Ago: The Evolution of Chemical Quantum Theory 17
3. The Molecular Electrostatic Potential as an Interpretative Tool for Intermolecular Interactions 22
4. Intermolecular Energy: A Full Decomposition at HF Level 50
5. Molecular Electrostatics and Semiclassical Approximation in Solvation Effects 83
Chapter 2. Molecular Electrostatic Potentials from Density Functional Theory 120
1. Introduction 120
2. Calculation of Electrostatic Observables 121
3. Simplified Analytic Expressions for the Molecular Electrostatic Potential 131
4. Critical Points of the Molecular Electrostatic Potential 140
5. Evolution of the Molecular Electrostatic Potential During Chemical Reactions 147
6. Conclusion 152
Chapter 3. The Use of Electrostatic Potential Fields in QSAR and QSPR 158
1. Introduction 158
2. QSAR and QSPR 161
3. EP–based 3D QSAR/QSPR approaches 171
4. Conclusions 190
Chapter 4. Generalization of the Molecular Electrostatic Potential for the Study of Noncovalent Interactions 196
1. Introduction 196
2. Introduction of Environment Effects in the MEP 198
3. Introduction of Non–Electrostatic Energy Terms in the MEP 205
4. Future Directions 225
Chapter 5. Molecular Recognition via Electrostatic Potential Topography 234
1. Introduction 234
2. Models for Weak Intermolecular Interactions 238
3. Topography of Molecular Scalar Fields 241
4. Topography–Based Molecular Interaction Model 253
Concluding Remarks 253
Chapter 6. Molecular Electrostatic Potentials and Fields: Hydrogen Bonding, Recognition, Reactivity and Modelling 272
1. Introduction 272
2. Definitions and Methods 273
3. Charge Distribution 277
4. Representation of MEP and MEF 282
5. Reactivity, Hydrogen Bonding and Other Properties 283
6. Recognition and Modelling 293
Chapter 7. Molecular Electrostatic Potentials for Large Systems 312
1. Introduction 312
2. Reactivity Concepts 313
3. Calculation of Cumulative Atomic Multipole Moments in SINDO1 318
4. Calculation of the MESP with SINDO1 320
5. The Molecular Surface 326
6. Silicon Clusters 327
7. Solid Silicon 337
8. Conclusions 344
Chapter 8. Protein Electrostatics 348
1. Introduction 348
2. Methodology 349
3. Applications 367
4. Conclusions 380
Chapter 9. The Lorentz–Debye–Sack Theory and Dielectric Screening of Electrostatic Effects in Proteins and Nucleic Acids 386
1. Introduction 386
2. Lorentz–Debye–Sack Theory of Polar Molecules and Radial Permittivity Profiles 389
3. Electrostatic Screening in Macromolecular Systems 397
4. Application of Electrostatic Screening to the Calculation of Equilibrium Properties 403
5. Electrostatic Screening in Molecular Dynamics and Monte Carlo Simulations 407
6. Conclusions 415
Chapter 10. Modelling Intrinsic Basicities: The Use of the Electrostatic Potentials and the Atoms-in-Molecules Theory 422
1. Introduction 422
2. Computational Details 425
3. Carbonyl vs. Thiocarbonyl Compounds 426
4. Three–Membered Rings 451
5. Concluding Remarks 467
Chapter 11. Computed Electrostatic Potentials in Molecules, Clusters, Solids and Biosystems Containing Transition Metals 472
1. Introduction 472
2. Lattice Energy and Cluster – Lattice Interaction in Ionic Crystals 473
3. Electrostatic Potentials as a Reactivity Index for Complex Ions and Molecules 483
4. Polar Molecules in Solution 507
5. Experimental Electrostatic Potentials 512
6. Conclusion 514
Chapter 12. Studies on the Molecular Electrostatic Potential Inside the Microporous Material and Its Relevance to their Catalytic Activity 524
1. Introduction 525
2. Methodology 526
3. Applications 527
4. Conclusions 553
Chapter 13. X–ray Diffraction and the Potential Distribution in Crystals 558
1. Introduction 558
2. Basic Theory 561
3. Multipole Analysis 569
4. Partitioning 576
5. Data Collection 579
6. Results 582
7. Comparison with Theory 591
Chapter 14. Molecular Electrostatic Potentials vs. DFT Descriptors of Reactivity 602
1. Introduction 602
2. DFT–Based Reactivity Descriptors: Conceptual and Methodological Issues 603
3. Results and Discussion 611
4. Conclusions 628
Chapter 15. Electrostatic Potential, Bond Density and Bond Order in Molecules and Clusters 634
1. Introduction 634
2. Electrostatic Potential at the Nucleus of a Neutral Atom Related to the Electronic Correlation Energies of Atomic Ions 635
3. Chemical Potential and Bond Mid-Point Properties 640
4. Cluster Properties 644
5. Dissociation of Doubly-Charged Clusters: Study of Supermolecular Ions (Na+20) 2 and (K+20)2 649
6. Bond Density and Chemical Network Model 653
7. Correlation Energy and Electron Density 655
Chapter 16. Relationships of Electrostatic Potentials to Intrinsic Molecular Properties 664
1. Introduction 664
2. Atomic and Molecular Energies as Functions of Electrostatic Potentials at Nuclei 664
3. Electrostatic Potentials and Chemical Potentials 667
4. Topographical Analyses 669
5. Lattice Energies and Ionic Radii 670
6. Covalent Radii and Bond Dissociation Energies 670
7. Electronic Densities and Electrostatic Potentials 672
Index 676