David Micha

Molecular Interactions

Concepts and Methods

• Gebundenes Buch

Produktbeschreibung

Presenting concepts, theory, and computational approaches, Molecular Interactions covers long, intermediate, and short range interactions of molecules in their ground electronic state, interactions of electronically excited species, interactions of extended systems (such as chains, clusters and surfaces), and interactions in liquids and solids. This modern, comprehensive treatment of intermolecular forces acquaints advanced undergraduate and beginning graduate students as well as researchers with orders of magnitude of properties, useful models, and the theory and computational aspects needed to interpret and predict phenomena.

Produktdetails

• Verlag: Wiley & Sons
• 1. Auflage
• Seitenzahl: 400
• Erscheinungstermin: 27. August 2019
• Englisch
• Abmessung: 229mm x 157mm x 23mm
• Gewicht: 757g
• ISBN-13: 9780470290743
• ISBN-10: 0470290749
• Artikelnr.: 26432746

Autorenporträt

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.

Inhaltsangabe

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 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 References 107 4 Model Potential Functions 111 4.1 Many-Atom Structures
111 4.2 Atom-Atom Potentials 114 4.2.1 Standard Models and Their Relations
114 4.2.2 Combination Rules 116 4.2.3 Very Short-Range Potentials 117 4.2.4
Local Parametrization of Potentials 117 4.3 Atom-Molecule and
Molecule-Molecule Potentials 119 4.3.1 Dependences on Orientation Angles
119 4.3.2 Potentials as Functionals of Variable Parameters 124 4.3.3
Hydrogen Bonding 124 4.3.4 Systems with Additive Anisotropic
Pair-Interactions 125 4.3.5 Bond Rearrangements 125 4.4 Interactions in
Extended (Many-Atom) Systems 127 4.4.1 Interaction Energies in Crystals 127
4.4.2 Interaction Energies in Liquids 131 4.5 Interaction Energies in a
Liquid Solution and in Physisorption 135 4.5.1 Potential Energy of a Solute
in a Liquid Solution 135 4.5.2 Potential Energies of Atoms and Molecules
Adsorbed at Solid Surfaces 139 4.6 Interaction Energies in Large Molecules
and in Chemisorption 143 4.6.1 Interaction Energies Among Molecular
Fragments 143 4.6.2 Potential Energy Surfaces and Force Fields in Large
Molecules 145 4.6.3 Potential Energy Functions of Global Variables
Parametrized with Machine Learning Procedures 148 References 152 5
Intermolecular States 157 5.1 Molecular Energies for Fixed Nuclear
Positions 158 5.1.1 Reference Frames 158 5.1.2 Energy Density Functionals
for Fixed Nuclei 160 5.1.3 Physical Contributions to the Energy Density
Functional 162 5.2 General Properties of Potentials 163 5.2.1 The
Electrostatic Force Theorem 163 5.2.2 Electrostatic Forces from Approximate
Wavefunctions 164 5.2.3 The Example of Hydrogenic Molecules 165 5.2.4 The
Virial Theorem 166 5.2.5 Integral Form of the Virial Theorem 168 5.3
Molecular States for Moving Nuclei 169 5.3.1 Expansion in an Electronic
Basis Set 169 5.3.2 Matrix Equations for Nuclear Amplitudes in Electronic
States 170 5.3.3 The Flux Function and Conservation of Probability 172 5.4
Electronic Representations 172 5.4.1 The Adiabatic Representation 172 5.4.2
Hamiltonian and Momentum Couplings from Approximate Adiabatic Wavefunctions
173 5.4.3 Nonadiabatic Representations 174 5.4.4 The Two-state Case 175
5.4.5 The Fixed-nuclei, Adiabatic, and Condon Approximations 176 5.5
Electronic Rearrangement for Changing Conformations 180 5.5.1 Construction
of Molecular Electronic States from Atomic States: Multistate Cases 180
5.5.2 The Noncrossing Rule 181 5.5.3 Crossings in Several Dimensions:
Conical Intersections and Seams 184 5.5.4 The Geometrical Phase and
Generalizations 189 References 192 6 Many-Electron Treatments 195 6.1
Many-Electron States 195 6.1.1 Electronic Exchange and Charge Transfer 195
6.1.2 Many-Electron Descriptions and Limitations 198 6.1.3 Properties and
Electronic Density Matrices 203 6.1.4 Orbital Basis Sets 205 6.2
Supermolecule Methods 209 6.2.1 The Configuration Interaction Procedure for
Molecular Potential Energies 209 6.2.2 Perturbation Expansions 215 6.2.3
Coupled-Cluster Expansions 218 6.3 Many-Atom Methods 222 6.3.1 The
Generalized Valence-Bond Method 222 6.3.2 Symmetry-Adapted Perturbation
Theory 225 6.4 The Density Functional Approach to Intermolecular Forces 228
6.4.1 Functionals for Interacting Closed- and Open-Shell Molecules 228
6.4.2 Electronic Exchange and Correlation from the Adiabatic-Connection
Relation 232 6.4.3 Issues with DFT, and the Alternative Optimized Effective
Potential Approach 238 6.5 Spin-Orbit Couplings and Relativistic Effects in
Molecular Interactions 243 6.5.1 Spin-Orbit Couplings 243 6.5.2 Spin-Orbit
Effects on Interaction Energies 245 References 247 7 Interactions Between
Two Many-Atom Systems 255 7.1 Long-range Interactions of Large Molecules
255 7.1.1 Interactions from Charge Density Operators 255 7.1.2
Electrostatic, Induction, and Dispersion Interactions 258 7.1.3 Population
Analyses of Charge and Polarization Densities 260 7.1.4 Long-range
Interactions from Dynamical Susceptibilities 262 7.2 Energetics of a Large
Molecule in a Medium 265 7.2.1 Solute-Solvent Interactions 265 7.2.2
Solvation Energetics for Short Solute-Solvent Distances 268 7.2.3 Embedding
of a Molecular Fragment and the QM/MM Treatment 270 7.3 Energies from
Partitioned Charge Densities 272 7.3.1 Partitioning of Electronic Densities
272 7.3.2 Expansions of Electronic Density Operators 274 7.3.3 Expansion in
a Basis Set of Localized Functions 277 7.3.4 Expansion in a Basis Set of
Plane Waves 279 7.4 Models of Hydrocarbon Chains and of Excited Dielectrics
281 7.4.1 Two Interacting Saturated Hydrocarbon Compounds: Chains and
Cyclic Structures 281 7.4.2 Two Interacting Conjugated Hydrocarbon Chains
284 7.4.3 Electronic Excitations in Condensed Matter 289 7.5 Density
Functional Treatments for All Ranges 291 7.5.1 Dispersion-Corrected Density
Functional Treatments 291 7.5.2 Long-range Interactions from Nonlocal
Functionals 294 7.5.3 Embedding of Atomic Groups with DFT 297 7.6
Artificial Intelligence Learning Methods for Many-Atom Interaction Energies
300 References 303 8 Interaction of Molecules with Surfaces 309 8.1
Interaction of a Molecule with a Solid Surface 309 8.1.1 Interaction
Potential Energies at Surfaces 309 8.1.2 Electronic States at Surfaces 314
8.1.3 Electronic Susceptibilities at Surfaces 319 8.1.4 Electronic
Susceptibilities for Metals and Semiconductors 321 8.2 Interactions with a
Dielectric Surface 324 8.2.1 Long-range Interactions 324 8.2.2 Short and
Intermediate Ranges 329 8.3 Continuum Models 332 8.3.1 Summations Over
Lattice Cell Units 332 8.3.2 Surface Electric Dipole Layers 333 8.3.3
Adsorbate Monolayers 335 8.4 Nonbonding Interactions at a Metal Surface 337
8.4.1 Electronic Energies for Varying Molecule-Surface Distances 337 8.4.2
Potential Energy Functions and Physisorption Energies 341 8.4.3 Embedding
Models for Physisorption 347 8.5 Chemisorption 349 8.5.1 Models of
Chemisorption 349 8.5.2 Charge Transfer at a Metal Surface 354 8.5.3
Dissociation and Reactions at a Metal Surface from Density Functionals 359
8.6 Interactions with Biomolecular Surfaces 363 References 367 Index 373