Molecular Interactions - David a Micha

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Résumé :

Preface xi

1 Fundamental Concepts 1

1.1 Molecular Interactions in Nature 2

1.2 Potential Energies for Molecular Interactions 4

1.2.1 The Concept of a Molecular Potential Energy 4

1.2.2 Theoretical Classification of Interaction Potentials 6

1.2.2.1 Small Distances 7

1.2.2.2 Intermediate Distances 8

1.2.2.3 Large Distances 8

1.2.2.4 Very Large Distances 8

1.3 Quantal Treatment and Examples of Molecular Interactions 9

1.4 Long-Range Interactions and Electrical Properties of Molecules 21

1.4.1 Electric Dipole of Molecules 21

1.4.2 Electric Polarizabilities of Molecules 22

1.4.3 Interaction Potentials from Multipoles 23

1.5 Thermodynamic Averages and Intermolecular Forces 24

1.5.1 Properties and Free Energies 24

1.5.2 Polarization in Condensed Matter 25

1.5.3 Pair Distributions and Potential of Mean-Force 26

1.6 Molecular Dynamics and Intermolecular Forces 27

1.6.1 Collisional Cross Sections 27

1.6.2 Spectroscopy of van der Waals Complexes and of Condensed Matter 28

1.7 Experimental Determination and Applications of Interaction Potential Energies 29

1.7.1 Thermodynamics Properties 30

1.7.2 Spectroscopy and Diffraction Properties 30

1.7.3 Molecular Beam and Energy Deposition Properties 30

1.7.4 Applications of Intermolecular Forces 31

References 31

2 Molecular Properties 35

2.1 Electric Multipoles of Molecules 35

2.1.1 Potential Energy of a Distribution of Charges 35

2.1.2 Cartesian Multipoles 36

2.1.3 Spherical Multipoles 37

2.1.4 Charge Distributions for an Extended System 38

2.2 Energy of a Molecule in an Electric Field 40

2.2.1 Quantal Perturbation Treatment 40

2.2.2 Static Polarizabilities 41

2.3 Dynamical Polarizabilities 43

2.3.1 General Perturbation 43

2.3.2 Periodic Perturbation Field 47

2.4 Susceptibility of an Extended Molecule 49

2.5 Changes of Reference Frame 52

2.6 Multipole Integrals from Symmetry 54

2.7 Approximations and Bounds for Polarizabilities 57

2.7.1 Physical Models 57

2.7.2 Closure Approximation and Sum Rules 58

2.7.3 Upper and Lower Bounds 59

References 60

3 Quantitative Treatment of Intermolecular Forces 63

3.1 Long Range Interaction Energies from Perturbation Theory 64

3.1.1 Interactions in the Ground Electronic States 64

3.1.2 Interactions in Excited Electronic States and in Resonance 68

3.2 Long Range Interaction Energies from Permanent and Induced Multipoles 68

3.2.1 Molecular Electrostatic Potentials 68

3.2.2 The Interaction Potential Energy at Large Distances 70

3.2.3 Electrostatic, Induction, and Dispersion Forces 73

3.2.4 Interacting Atoms and Molecules from Spherical Components of Multipoles 75

3.2.5 Interactions from Charge Densities and their Fourier Components 76

3.3 Atom-Atom, Atom-Molecule, and Molecule-Molecule Long-Range Interactions 78

3.3.1 Example of Li⁺+Ne 78

3.3.2 Interaction of Oriented Molecular Multipoles 79

3.3.3 Example of Li⁺+HF 80

3.4 Calculation of Dispersion Energies 81

3.4.1 Dispersion Energies from Molecular Polarizabilities 81

3.4.2 Combination Rules 82

3.4.3 Upper and Lower Bounds 83

3.4.4 Variational Calculation of Perturbation Terms 86

3.5 Electron Exchange and Penetration Effects at Reduced Distances 87

3.5.1 Quantitative Treatment with Electronic Density Functionals 87

3.5.2 Electronic Rearrangement and Polarization 93

3.5.3 Treatments of Electron...

Biographie:
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Sommaire:

David A. Micha, PhD, is a Professor of Chemistry and Physics at the University of Florida, presently Adjunct and Emeritus, with continuing research activity. His many research interests include molecular interactions and kinetics, and quantum molecular dynamics involving energy transfer, electron transfer, light emission, reactions in gas phase collisions, and also at solid surfaces. His work has been recognized with awards from the Alfred P. Sloan Foundation and the Dreyfus Foundation, and with an Alexander von Humboldt Senior Scientist Award. Dr. Micha has been the organizer of several Pan-American Workshops and is a co-organizer of the Sanibel Symposium on Theory and Computation for the Molecular and Materials Sciences at the University of Florida.