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