Intermolecular and Surface Forces

Intermolecular and Surface Forces

3rd Edition - June 13, 2011

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  • Author: Jacob Israelachvili
  • Hardcover ISBN: 9780123919274
  • eBook ISBN: 9780123919335

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Intermolecular and Surface Forces describes the role of various intermolecular and interparticle forces in determining the properties of simple systems such as gases, liquids and solids, with a special focus on more complex colloidal, polymeric and biological systems. The book provides a thorough foundation in theories and concepts of intermolecular forces, allowing researchers and students to recognize which forces are important in any particular system, as well as how to control these forces. This third edition is expanded into three sections and contains five new chapters over the previous edition.

Key Features

  • Starts from the basics and builds up to more complex systems
  • Covers all aspects of intermolecular and interparticle forces both at the fundamental and applied levels
  • Multidisciplinary approach: bringing together and unifying phenomena from different fields
  • This new edition has an expanded Part III and new chapters on non-equilibrium (dynamic) interactions, and tribology (friction forces)


Research workers and students in materials science, especially in biomaterials and polymers, and applied physicists working in these fields

Table of Contents

  • Fundamental Constants

    Intermolecular and Surface Forces


    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 ψx and Ionic Concentrations ρx 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



Product details

  • No. of pages: 704
  • Language: English
  • Copyright: © Academic Press 2011
  • Published: June 13, 2011
  • Imprint: Academic Press
  • Hardcover ISBN: 9780123919274
  • eBook ISBN: 9780123919335

About the Author

Jacob Israelachvili

Affiliations and Expertise

University of California, Santa Barbara

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