Fundamental Constants
Intermolecular and Surface Forces
Copyright
Preface to the Third Edition
Preface to Second Edition
Preface to the First Edition
Units, Symbols, Useful Quantities and Relations
Definitions and Glossary
1. Historical Perspective
1.1. The Four Forces of Nature
1.2. Greek and Medieval Notions of Intermolecular Forces
1.3. The Seventeenth Century: First Scientific Period
1.4. The Eighteenth Century: Confusion, Contradictions, and Controversy
1.5. The Nineteenth Century: Continuum versus Molecular Theories
1.6. Intermolecular Force-Laws and Interaction Potentials: Long- and Short-Range Forces
1.7. First Successful Phenomenological Theories
1.8. First Estimates of Molecular Sizes
1.9. The Twentieth Century: Understanding Simple Systems
1.10. Recent Trends
2. Thermodynamic and Statistical Aspects of Intermolecular Forces
2.1. The Interaction of Molecules in Free Space and in a Medium
2.2. Self-Energy and Pair Potential
2.3. The Boltzmann Distribution and the Chemical Potential
2.4. The Distribution of Molecules and Particles in Systems at Equilibrium
2.5. The Van der Waals Equation of State (EOS)
2.6. The Criterion of the Thermal Energy kT for Gauging the Strength of an Interaction
2.7. Classification of Forces and Pair Potentials
2.8. Theoretical Analyses of Multimolecular Systems: Continuum and Molecular Approaches
2.9. Molecular Approaches via Computer Simulations: Monte Carlo (MC) and Molecular Dynamics (MD)
2.10. Newton’s Laws Applied to Two-Body Collisions
2.11. Kinetic and Statistical Aspects of Multiple Collisions: the Boltzmann Distribution
Chapter 3. Strong Intermolecular Forces
3.1. Covalent or Chemical Bonding Forces
3.2. Physical and Chemical Bonds
3.3. Coulomb Forces or Charge-Charge Interactions, Gauss’s Law
3.4. Ionic Crystals
3.5. Reference States
3.6. Range of Electrostatic Forces
3.7. The Born Energy of an Ion
3.8. Solubility of Ions in Different Solvents
3.9. Specific Ion-Solvent Effects: Continuum Approach
3.10. Molecular Approach: Computer Simulations and Integral Equations of Many-Body Systems
4. Interactions Involving Polar Molecules
4.1. What Are Polar Molecules?
4.2. Dipole Self-Energy
4.3. Ion-Dipole Interactions
4.4. Ions in Polar Solvents
4.5. Strong Ion-Dipole Interactions in Water: Hydrated Ions
4.6. Solvation Forces, Structural Forces, and Hydration Forces
4.7. Dipole-Dipole Interactions
4.9. Hydrogen Bonds
4.10. Rotating Dipoles and Angle-Averaged Potentials
4.11. Entropic Effects
5. Interactions Involving the Polarization of Molecules
5.1. The Polarizability of Atoms and Molecules
5.2. The Polarizability of Polar Molecules
5.3. Other Polarization Mechanisms and the Effects of Polarization on Electrostatic Interactions
5.4. Interactions between Ions and Uncharged Molecules
5.5. Ion-Solvent Molecule Interactions and the Born Energy
5.6. Dipole-Induced Dipole Interactions
5.7. Unification of Polarization Interactions
5.8. Solvent Effects and “Excess Polarizabilities¿
6. Van der Waals Forces
6.1. Origin of the Van der Waals-dispersion Force between Neutral Molecules: the London Equation
6.2. Strength of Dispersion Forces: Van der Waals Solids and Liquids
6.3. Van der Waals Equation of State
6.4. Gas-Liquid and Liquid-Solid Phase Transitions in 3D and 2D
6.5. Van der Waals Forces between Polar Molecules
6.6. General Theory of Van der Waals Forces between Molecules
6.7. Van der Waals Forces in a Medium
6.8. Dispersion Self-Energy of a Molecule in a Medium
6.9. Further Aspects of Van der Waals Forces: Anisotropy (Orientation), Nonadditivity (Many-Body), and Retardation Effects
7. Repulsive Steric Forces, Total Intermolecular Pair Potentials, and Liquid Structure
7.1. Sizes of Atoms, Molecules, and Ions
7.2. Repulsive Potentials
7.3. Total Intermolecular Pair Potentials: Their Form, Magnitude, and Range
7.4. Role of Repulsive Forces in Noncovalently Bonded Solids
7.5. Packing of Molecules and Particles in Solids
7.6. Role of Repulsive Forces in Liquids: Liquid Structure
7.7. The Effect of Liquid Structure on Molecular Forces
8. Special Interactions
8.1. The Unique Properties of Water
8.2. The Hydrogen Bond
8.3. Models of Water and Associated Liquids
8.4. Relative Strengths of Different Types of Interactions
8.5. The Hydrophobic Effect
8.6. The Hydrophobic Interaction
8.7. Hydrophilic Interactions
9. Nonequilibrium and Time-Dependent Interactions
9.1. Time- and Rate-Dependent Interactions and Processes
9.2. Rate- and Time-Dependent Detachment (Debonding) Forces
9.3. Energy Transfer (Dissipation) during Molecular Collisions: the Deborah Number
9.4. Energy Transfer during Cyclic Bonding-Unbonding Processes
9.5. Relationships between Time, Temperature, and Velocity (Rate) in Complex Processes
10. Unifying Concepts in Intermolecular and Interparticle Forces
10.1. The Association of Like Molecules or Particles in a Medium
10.2. Two Like Surfaces Coming Together in a Medium: Surface and Interfacial Energy
10.3. The Association of Unlike Molecules, Particles, or Surfaces in a Third Medium
10.4. Particle-Surface and Particle-Interface Interactions
10.5. Engulfing and Ejection
10.6. Adsorbed Surface Films: Wetting and Nonwetting
11. Contrasts between Intermolecular, Interparticle, and Intersurface Forces
11.1. Short-Range and Long-Range Effects of a Force: Qualitative Differences in the Interactions of Particles and Small Molecules
11.2. Interaction Potentials between Macroscopic Bodies
11.3. Effective Interaction Area of Two Spheres: the Langbein Approximation
11.4. Interactions of Particles Compared to Those between Atoms or Small Molecules
11.5. Interaction Energies and Interaction Forces: the Derjaguin Approximation
11.6. “Body Forces¿ and “Surface Forces¿
Chapter 12. Force-Measuring Techniques
12.1. Direct and Indirect Measurements of Intermolecular, Interparticle, and Surface Forces
12.2. Different Direct Force-Measuring Techniques
12.3. Mechanics of Direct Force Measurements and Problems of Interpretation
12.4. Measuring Force-Distance Functions, F(D)
12.5. Instabilities
12.6. Measuring Adhesion Forces and Energies
12.7. Measuring Forces between Macroscopic Surfaces: the SFA, OP/OS and Related Techniques
12.8. Measuring Forces between Microscopic (Colloidal) and Nanoscopic Particles: AFM and TIRM Techniques
12.9. Measuring Single-Molecule and Single-Bond Interactions: OT and MC Techniques
Chapter 13. Van der Waals Forces between Particles and Surfaces
13.1. Van der Waals Force-Laws for Bodies of Different Geometries: the Hamaker Constant
13.2. Strength of Van der Waals Forces between Bodies in a Vacuum or Air
13.3. The Lifshitz Theory of Van der Waals Forces
13.4. Particle-Surface Interactions
13.5. Nonretarded Hamaker Constants Calculated on the Basis of the Lifshitz Theory
13.6. Van der Waals Forces between Conducting Media
13.7. Theoretical and Experimental Hamaker Constants for Interactions in a Vacuum or Air
13.8. Applications of the Lifshitz Theory to Interactions in a Medium
13.9. Repulsive Van der Waals Forces: Disjoining Pressure and Wetting Films
13.10. Van der Waals Forces at Large Separations: Retardation Effects
13.11. Electrostatic Screening Effects in Electrolyte Solutions
13.12. Combining Relations
13.13. Surface and Adhesion Energies
13.14. Surface Energies of Metals
13.15. Forces between Surfaces with Adsorbed Layers
13.16. Experiments on Van der Waals Forces
14. Electrostatic Forces between Surfaces in Liquids
14.1. The Charging of Surfaces in Liquids: the Electric “Double-Layer¿
14.2. Charged Surfaces in Water: No Added Electrolyte—“Counterions Only¿
14.3. The Poisson-Boltzmann (PB) Equation
14.4. Surface Charge, Electric Field, and Counterion Concentration at a Surface: “Contact¿ Values
14.5. Counterion Concentration Profile Away from a Surface
14.6. Origin of the Ionic Distribution, Electric Field, Surface Potential, and Pressure
14.7. The Pressure between Two Charged Surfaces in Water: the Contact Value Theorem
14.8. Limit of Large Separations: Thick Wetting Films
14.9. Limit of Small Separations: Osmotic Limit and Charge Regulation
14.10. Charged Surfaces in Electrolyte Solutions
14.11. The Grahame Equation
14.12. Surface Charge and Potential of Isolated Surfaces
14.13. Effect of Divalent Ions
14.14. The Debye Length
14.15. Variation of Potential ?x and Ionic Concentrations ?x Away from a Surface
14.16. Electrostatic Double-Layer Interaction Forces and Energies between Various Particle Surfaces
14.17. Exact Solutions for Constant Charge and Constant Potential Interactions: Charge Regulation
14.18. Asymmetric Surfaces
14.19. Ion-Condensation and Ion-Correlation Forces
14.20. More Complex Systems: Finite Reservoir Systems and Finite Ion-Size Effects
14.21. Van der Waals and Double-Layer Forces Acting Together: the DLVO Theory
14.22. Experimental Measurements of Double-Layer and DLVO Forces
14.23. Electrokinetic Forces
14.24. Discrete Surface Charges and Dipoles
15. Solvation, Structural, and Hydration Forces
15.1. Non-DLVO Forces
15.2. Molecular Ordering at Surfaces, Interfaces, and in Thin Films
15.3. Ordering of Spherical Molecules between Two Smooth (Unstructured) Surfaces
15.4. Ordering of Nonspherical Molecules between Structured Surfaces
15.5. Origin of Main Type of Solvation Force: the Oscillatory Force
15.6. Jamming
15.7. Experimental Measurements and Properties of Oscillatory Forces
15.8. Solvation Forces in Aqueous Systems: Monotonically Repulsive “Hydration¿ Forces
15.9. Solvation Forces in Aqueous Systems: Attractive “Hydrophobic¿ Forces
16. Steric (Polymer-Mediated) and Thermal Fluctuation Forces
16.1. Diffuse Interfaces in Liquids
16.2. The States of Polymers in Solution and at Surfaces
16.3. Repulsive “Steric¿ or “Overlap¿ Forces between Polymer-Covered Surfaces
16.4. Interparticle Forces in Pure Polymer Liquids (Polymer Melts)
16.5. Attractive “Intersegment¿ and “Bridging¿ Forces
16.6. Attractive “Depletion¿ Forces
16.7. Polyelectrolytes
16.8. Nonequilibrium Aspects of Polymer Interactions
16.9. Thermal Fluctuations of and Forces between Fluid-Like Interfaces
16.10. Short-Range Protrusion Forces
16.11. Long-Range Undulation Forces
17. Adhesion and Wetting Phenomena
17.1. Surface and Interfacial Energies
17.2. Adhesion Energies versus Adhesion Forces
17.3. Highly Curved Surfaces and Interfaces: Clusters, Cavities, and Nanoparticles
17.4. Contact Angles and Wetting Films
17.5. Wetting of Rough, Textured, and Chemically Heterogeneous Surfaces
17.6. Contact Angle Hysteresis
17.7. Adhesion of Solid Particles: the JKR and Hertz Theories
17.8. Adhesion Hysteresis
17.9. Adhesion of Rough and Textured Surfaces
17.10. Plastic Deformations
17.11. Capillary Forces
18. Friction and Lubrication Forces
18.1. Origin of Friction and Lubrication Forces
18.2. Relationship between Adhesion and Friction Forces
18.3. Amontons’ Laws of (Dry) Friction
18.4. Smooth and Stick-Slip Sliding
18.5. Lubricated Sliding
18.6. Transitions between Liquid- and Solid-Like Films
18.7. The “Real¿ Area of Contact of Rough Surfaces
18.8. Rolling Friction
18.9. Theoretical Modeling of Friction Mechanisms
19. Thermodynamic Principles of Self-Assembly
19.1. Introduction: Soft Structures
19.2. Fundamental Thermodynamic Equations of Self-Assembly
19.3. Conditions Necessary for the Formation of Aggregates
19.4. Effect of Dimensionality and Geometry: Rods, Discs, and Spheres
19.5. The Critical Micelle Concentration (CMC)
19.6. Infinite Aggregates (Phase Separation) versus Finite Sized Aggregates (Micellization)
19.7. Hydrophobic Energy of Transfer
19.8. Nucleation and Growth of Aggregates
19.9. 2D Structures on Surfaces: Soluble and Insoluble Monolayers
19.10. Line Tension and 2D Micelles (Domains)
19.11. Soluble Monolayers and the Gibbs Adsorption Isotherm
19.12. Size Distributions of Self-Assembled Structures
19.13. Large and More Complex Amphiphilic Structures
19.14. Effects of Interactions between Aggregates: Mesophases and Multilayers
20. Soft and Biological Structures
20.1. Introduction: Equilibrium Considerations of Fluid Amphiphilic Structures
20.2. Optimal Headgroup Area
20.3. Geometric Packing Considerations
20.4. Spherical Micelles
20.5. Nonspherical and Cylindrical Micelles
20.6. Bilayers
20.7. Vesicles
20.8. Curvature/Bending Energies and Elasticities of Monolayers and Bilayers
20.9. Other Amphiphilic Structures and the Transitions between Them
20.10. Self-Assembly on Surfaces and Interfaces: 2D Micelles, Domains, and Rafts
20.11. Biological Membranes
20.12. Membrane Lipids
20.13. Membrane Proteins and Membrane Structure
21. Interactions of Biological Membranes and Structures
21.1. Van der Waals Forces
21.2. Electrostatic (Double-Layer) and DLVO Forces
21.3. Repulsive Entropic (Thermal Fluctuation, Steric-Hydration) Forces: Protrusion, Headgroup Overlap, and Undulation Forces
21.4. Attractive Depletion Forces
21.5. Attractive Hydrophobic Forces
21.6. Biospecificity: Complementary, Site-Specific and Ligand-Receptor (LR) Interactions
21.7. Bridging (Tethering) Forces
21.8. Interdependence of Intermembrane and Intramembrane Forces
21.9. Biomembrane Adhesion, Bioadhesion
21.10. Membrane Fusion
22. Dynamic Biointeractions
22.1. Subtleties of Biological Forces and Interactions
22.2. Interactions that Evolve in Space and Time: Some General Considerations
22.3. Biological Rupture and Capture: the Bell and Jarzynski Equations
22.4. Multiple Bonds in Series and in Parallel
22.5. Detachment versus Capture Processes: Biological Importance of “Rare Events¿
22.6. Dynamic Interactions between Biological Membranes and Biosurfaces
22.7. Self-Assembly versus Directed Assembly: Dynamic Phases and Tunable Materials
22.8. Motor Proteins, Transport Proteins, and Protein Engines
References
Index
