Molecular Interactions

A modern, comprehensive text and reference describing intermolecular forces, this book begins with coverage of the concepts and methods for simpler systems, then moves on to more advanced subjects for complex systems - emphasizing concepts and methods used in calculations with realistic models and compared with empirical data.

• Contains applications to many physical systems and worked examples

• Proceeds from introductory material to advanced modern treatments

• Has relevance for new materials, biological phenomena, and energy and fuels production

Auteur

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.

Texte du rabat

An up-to-date and comprehensive text that explores intermolecular forces

Molecular Interactions offers a comprehensive guide that examines the fundamental concepts and methods of intermolecular forces. The text provides a quantitative treatment based on molecular properties, introducing realistic models and theoretical tools needed to obtain physical properties. All chapters include an introduction to the qualitative aspects of molecular interactions and then explore the interactions are treated in a quantitative fashion.

The authora noted expert on the topicexamines the concepts and quantitative aspects of molecular interaction such as electrostatic, induction, and dispersion forces and shows how they extend to intermediate and short ranges for ground and excited states. The text includes a survey of model potential functions. It offers an exploration of recent developments in the field including electronically non-adiabatic interactions, correlated many-electron treatments, generalized density functional theory, decomposition, and embedding of molecular fragments for large systems. It also presents the most recent developments using artificial intelligence with network training for many-atom system. It includes molecular interactions between two many-atom systems, interactions in condensed matter, and interactions of molecules with surfaces.

• Presents the concepts and methods of molecular interactions used in calculations
• Offers comprehensive descriptions starting from atomic structure
• Provides the theory and computational approaches needed for many-atom interactions
• Contains illustrative applications to many physical systems and worked examples
  Written for students and researchers in chemical physics, materials sciences, molecular biology, pharmaceuticals, and medical sciences, Molecular Interactions offers an authoritative guide to the fundamentalconcepts and methods as well as information on the most recent innovations that have relevance for new materials, biological phenomena, and energy and fuels production.

Contenu

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 AtomAtom, AtomMolecule, and MoleculeMolecule 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 Electronic Exchange and Charge Transfer 98

3.6 Spin-orbit Couplings and Retardation Effects 102

3.7 Interactions in Three-Body and Many-Body Systems 103

3.7.1 Three-Body Systems 103

3.7.2 Many-Body Systems 106 &lt...