Intermolecular and Surface Forces, Third Edition

This reference 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. · 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) Fundamental Constants ......Page 2 Intermolecular and Surface Forces......Page 5 Copyright......Page 6 Contents......Page 7 Preface to the Third Edition......Page 19 Preface to Second Edition......Page 21 Preface to the First Edition......Page 23 Units, Symbols, Useful Quantities and Relations......Page 25 Definitions and Glossary......Page 31 PART I - The Forces between Atoms and Molecules......Page 33 1.2 Greek and Medieval Notions of Intermolecular Forces......Page 35 1.3 The Seventeenth Century: First Scientific Period......Page 37 1.4 The Eighteenth Century: Confusion, Contradictions, and Controversy......Page 39 1.5 The Nineteenth Century: Continuum versus Molecular Theories......Page 40 1.6 Intermolecular Force-Laws and Interaction Potentials: Long- and Short-Range Forces......Page 41 1.7 First Successful Phenomenological Theories......Page 44 1.8 First Estimates of Molecular Sizes......Page 47 1.9 The Twentieth Century: Understanding Simple Systems......Page 48 1.10 Recent Trends......Page 49 Problems and Discussion Topics......Page 50 2.1 The Interaction of Molecules in Free Space and in a Medium......Page 55 2.2 Self-Energy and Pair Potential......Page 57 2.3 The Boltzmann Distribution and the Chemical Potential......Page 58 2.4 The Distribution of Molecules and Particles in Systems at Equilibrium......Page 59 2.5 The Van der Waals Equation of State (EOS)......Page 62 2.6 The Criterion of the Thermal Energy kT for Gauging the Strength of an Interaction......Page 63 2.7 Classification of Forces and Pair Potentials......Page 66 2.8 Theoretical Analyses of Multimolecular Systems: Continuum and Molecular Approaches......Page 67 2.9 Molecular Approaches via Computer Simulations: Monte Carlo (MC) and Molecular Dynamics (MD)......Page 69 2.10 Newton’s Laws Applied to Two-Body Collisions......Page 71 2.11 Kinetic and Statistical Aspects of Multiple Collisions: the Boltzmann Distribution......Page 75 Problems and Discussion Topics......Page 81 3.1 Covalent or Chemical Bonding Forces......Page 85 3.2 Physical and Chemical Bonds......Page 86 3.3 Coulomb Forces or Charge-Charge Interactions, Gauss’s Law......Page 87 3.4 Ionic Crystals......Page 90 3.5 Reference States......Page 91 3.6 Range of Electrostatic Forces......Page 92 3.7 The Born Energy of an Ion......Page 93 3.8 Solubility of Ions in Different Solvents......Page 94 3.9 Specific Ion-Solvent Effects: Continuum Approach......Page 98 3.10 Molecular Approach: Computer Simulations and Integral Equations of Many-Body Systems......Page 99 Problems and Discussion Topics......Page 100 4.1 What Are Polar Molecules?......Page 103 4.3 Ion-Dipole Interactions......Page 105 4.5 Strong Ion-Dipole Interactions in Water: Hydrated Ions......Page 110 4.6 Solvation Forces, Structural Forces, and Hydration Forces......Page 112 4.7 Dipole-Dipole Interactions......Page 113 4.9 Hydrogen Bonds......Page 115 4.10 Rotating Dipoles and Angle-Averaged Potentials......Page 116 4.11 Entropic Effects......Page 118 Problems and Discussion Topics......Page 120 5.1 The Polarizability of Atoms and Molecules......Page 123 5.2 The Polarizability of Polar Molecules......Page 125 5.3 Other Polarization Mechanisms and the Effects of Polarization on Electrostatic Interactions......Page 126 5.4 Interactions between Ions and Uncharged Molecules......Page 128 5.5 Ion-Solvent Molecule Interactions and the Born Energy......Page 130 5.7 Unification of Polarization Interactions......Page 131 5.8 Solvent Effects and “Excess Polarizabilities”......Page 132 Problems and Discussion Topics......Page 137 6.1 Origin of the Van der Waals-dispersion Force between Neutral Molecules: the London Equation......Page 139 6.2 Strength of Dispersion Forces: Van der Waals Solids and Liquids......Page 141 6.3 Van der Waals Equation of State......Page 145 6.4 Gas-Liquid and Liquid-Solid Phase Transitions in 3D and 2D......Page 147 6.5 Van der Waals Forces between Polar Molecules......Page 149 6.6 General Theory of Van der Waals Forces between Molecules......Page 151 6.7 Van der Waals Forces in a Medium......Page 154 6.8 Dispersion Self-Energy of a Molecule in a Medium......Page 158 6.9 Further Aspects of Van der Waals Forces: Anisotropy (Orientation), Nonadditivity (Many-Body), and Retardation Effects......Page 159 Problems and Discussion Topics......Page 162 7.1 Sizes of Atoms, Molecules, and Ions......Page 165 7.3 Total Intermolecular Pair Potentials: Their Form, Magnitude, and Range......Page 168 7.4 Role of Repulsive Forces in Noncovalently Bonded Solids......Page 172 7.5 Packing of Molecules and Particles in Solids......Page 174 7.6 Role of Repulsive Forces in Liquids: Liquid Structure......Page 177 7.7 The Effect of Liquid Structure on Molecular Forces......Page 179 Problems and Discussion Topics......Page 180 8.1 The Unique Properties of Water......Page 183 8.2 The Hydrogen Bond......Page 184 8.3 Models of Water and Associated Liquids......Page 188 8.4 Relative Strengths of Different Types of Interactions......Page 189 8.5 The Hydrophobic Effect......Page 190 8.6 The Hydrophobic Interaction......Page 193 8.7 Hydrophilic Interactions......Page 195 Problems and Discussion Topics......Page 198 9.1 Time- and Rate-Dependent Interactions and Processes......Page 201 9.2 Rate- and Time-Depended Detachment (Debonding) Forces......Page 203 9.3 Energy Transfer (Dissipation) during Molecular Collisions: the Deborah Number......Page 207 9.4 Energy Transfer during Cyclic Bonding-Unbonding Processes......Page 210 9.5 Relationships between Time, Temperature, and Velocity (Rate) in Complex Processes......Page 214 Problems and Discussion Topics......Page 217 PART II - The Forces between Particles and Surfaces......Page 221 10.1 The Association of Like Molecules or Particles in a Medium......Page 223 10.2 Two Like Surfaces Coming Together in a Medium: Surface and Interfacial Energy......Page 228 10.3 The Association of Unlike Molecules, Particles, or Surfaces in a Third Medium......Page 229 10.4 Particle-Surface and Particle-Interface Interactions......Page 230 10.5 Engulfing and Ejection......Page 232 10.6 Adsorbed Surface Films: Wetting and Nonwetting......Page 233 Problems and Discussion Topics......Page 235 11.1 Short-Range and Long-Range Effects of a Force: Qualitative Differences in the Interactions of Particles and Small Molecules......Page 237 11.2 Interaction Potentials between Macroscopic Bodies......Page 240 11.3 Effective Interaction Area of Two Spheres: the Langbein Approximation......Page 243 11.4 Interactions of Particles Compared to Those between Atoms or Small Molecules......Page 244 11.5 Interaction Energies and Interaction Forces: the Derjaguin Approximation......Page 247 Problems and Discussion Topics......Page 252 12.1 Direct and Indirect Measurements of Intermolecular, Interparticle, and Surface Forces......Page 255 12.2 Different Direct Force-Measuring Techniques......Page 259 12.3 Mechanics of Direct Force Measurements and Problems of Interpretation......Page 263 12.4 Measuring Force-Distance Functions, F(D)......Page 266 12.5 Instabilities......Page 267 12.6 Measuring Adhesion Forces and Energies......Page 269 12.7 Measuring Forces between Macroscopic Surfaces: the SFA, OP/OS and Related Techniques......Page 271 12.8 Measuring Forces between Microscopic (Colloidal) and Nanoscopic Particles: AFM and TIRM Techniques......Page 277 12.9 Measuring Single-Molecule and Single-Bond Interactions: OT and MC Techniques......Page 280 Problems And Discussion Topics......Page 282 13.1 Van der Waals Force-Laws for Bodies of Different Geometries: the Hamaker Constant......Page 285 13.2 Strength of Van der Waals Forces between Bodies in a Vacuum or Air......Page 287 13.3 The Lifshitz Theory of Van der Waals Forces......Page 288 13.4 Particle-Surface Interactions......Page 291 13.5 Nonretarded Hamaker Constants Calculated on the Basis of the Lifshitz Theory......Page 292 13.6 Van der Waals Forces between Conducting Media......Page 293 13.7 Theoretical and Experimental Hamaker Constants for Interactions in a Vacuum or Air......Page 295 13.8 Applications of the Lifshitz Theory to Interactions in a Medium......Page 296 13.9 Repulsive Van der Waals Forces: Disjoining Pressure and Wetting Films......Page 299 13.10 Van der Waals Forces at Large Separations: Retardation Effects......Page 302 13.12 Combining Relations......Page 306 13.13 Surface and Adhesion Energies......Page 307 13.14 Surface Energies of Metals......Page 312 13.15 Forces between Surfaces with Adsorbed Layers......Page 313 13.16 Experiments on Van der Waals Forces......Page 314 Problems and Discussion Topics......Page 316 14.1 The Charging of Surfaces in Liquids: the Electric “Double-Layer”......Page 323 14.3 The Poisson-Boltzmann (PB) Equation......Page 325 14.4 Surface Charge, Electric Field, and Counterion Concentration at a Surface: “Contact” Values......Page 326 14.5 Counterion Concentration Profile Away from a Surface......Page 328 14.6 Origin of the Ionic Distribution, Electric Field, Surface Potential, and Pressure......Page 330 14.7 The Pressure between Two Charged Surfaces in Water: the Contact Value Theorem......Page 332 14.8 Limit of Large Separations: Thick Wetting Films......Page 335 14.9 Limit of Small Separations: Osmotic Limit and Charge Regulation......Page 337 14.10 Charged Surfaces in Electrolyte Solutions......Page 338 14.11 The Grahame Equation......Page 340 14.12 Surface Charge and Potential of Isolated Surfaces......Page 341 14.13 Effect of Divalent Ions......Page 343 14.14 The Debye Length......Page 344 14.15 Variation of Potential ψx and Ionic Concentrations ρx Away from a Surface......Page 345 14.16 Electrostatic Double-Layer Interaction Forces and Energies between Various Particle Surfaces......Page 346 14.17 Exact Solutions for Constant Charge and Constant Potential Interactions: Charge Regulation......Page 350 14.18 Asymmetric Surfaces......Page 353 14.19 Ion-Condensation and Ion-Correlation Forces......Page 354 14.20 More Complex Systems: Finite Reservoir Systems and Finite Ion-Size Effects......Page 357 14.21 Van der Waals and Double-Layer Forces Acting Together: the DLVO Theory......Page 358 14.22 Experimental Measurements of Double-Layer and DLVO Forces......Page 363 14.23 Electrokinetic Forces......Page 366 14.24 Discrete Surface Charges and Dipoles......Page 367 Problems and Discussion Topics......Page 370 15.1 Non-DLVO Forces......Page 373 15.2 Molecular Ordering at Surfaces, Interfaces, and in Thin Films......Page 374 15.3 Ordering of Spherical Molecules between Two Smooth (Unstructured) Surfaces......Page 377 15.4 Ordering of Nonspherical Molecules between Structured Surfaces......Page 379 15.5 Origin of Main Type of Solvation Force: the Oscillatory Force......Page 381 15.6 Jamming......Page 386 15.7 Experimental Measurements and Properties of Oscillatory Forces......Page 387 15.8 Solvation Forces in Aqueous Systems: Monotonically Repulsive “Hydration” Forces......Page 393 15.9 Solvation Forces in Aqueous Systems: Attractive “Hydrophobic” Forces......Page 402 Problems and Discussion Topics......Page 410 16.2 The States of Polymers in Solution and at Surfaces......Page 413 16.3 Repulsive “Steric” or “Overlap” Forces between Polymer-Covered Surfaces......Page 419 16.4 Interparticle Forces in Pure Polymer Liquids (Polymer Melts)......Page 425 16.5 Attractive “Intersegment” and “Bridging” Forces......Page 426 16.6 Attractive “Depletion” Forces......Page 430 16.7 Polyelectrolytes......Page 434 16.8 Nonequilibrium Aspects of Polymer Interactions......Page 436 16.9 Thermal Fluctuations of and Forces between Fluid-Like Interfaces......Page 437 16.10 Short-Range Protrusion Forces......Page 438 16.11 Long-Range Undulation Forces......Page 440 Problems And Discussion Topics......Page 443 17.1 Surface and Interfacial Energies......Page 447 17.2 Adhesion Energies versus Adhesion Forces......Page 451 17.3 Highly Curved Surfaces and Interfaces: Clusters, Cavities, and Nanoparticles......Page 454 17.4 Contact Angles and Wetting Films......Page 461 17.5 Wetting of Rough, Textured, and Chemically Heterogeneous Surfaces......Page 466 17.6 Contact Angle Hysteresis......Page 471 17.7 Adhesion of Solid Particles: the JKR and Hertz Theories......Page 474 17.8 Adhesion Hysteresis......Page 480 17.9 Adhesion of Rough and Textured Surfaces......Page 484 17.10 Plastic Deformations......Page 485 17.11 Capillary Forces......Page 488 Problems and Discussion Topics......Page 493 18.1 Origin of Friction and Lubrication Forces......Page 501 18.2 Relationship between Adhesion and Friction Forces......Page 507 18.3 Amontons’ Laws of (Dry) Friction......Page 513 18.4 Smooth and Stick-Slip Sliding......Page 514 18.5 Lubricated Sliding......Page 517 18.6 Transitions between Liquid- and Solid-Like Films......Page 521 18.7 The “Real” Area of Contact of Rough Surfaces......Page 525 18.8 Rolling Friction......Page 526 18.9 Theoretical Modeling of Friction Mechanisms......Page 527 Problems and Discussion Topics......Page 529 PART III - Self-Assembling Structures and Biological Systems......Page 533 19.1 Introduction: Soft Structures......Page 535 19.2 Fundamental Thermodynamic Equations of Self-Assembly......Page 536 19.3 Conditions Necessary for the Formation of Aggregates......Page 541 19.4 Effect of Dimensionality and Geometry: Rods, Discs, and Spheres......Page 542 19.5 The Critical Micelle Concentration (CMC)......Page 544 19.6 Infinite Aggregates (Phase Separation) versus Finite Sized Aggregates (Micellization)......Page 545 19.7 Hydrophobic Energy of Transfer......Page 546 19.8 Nucleation and Growth of Aggregates......Page 547 19.9 2D Structures on Surfaces: Soluble and Insoluble Monolayers......Page 552 19.10 Line Tension and 2D Micelles (Domains)......Page 553 19.12 Size Distributions of Self-Assembled Structures......Page 556 19.13 Large and More Complex Amphiphilic Structures......Page 559 19.14 Effects of Interactions between Aggregates: Mesophases and Multilayers......Page 560 Problems and Discussion Topics......Page 562 20.1 Introduction: Equilibrium Considerations of Fluid Amphiphilic Structures......Page 567 20.2 Optimal Headgroup Area......Page 568 20.3 Geometric Packing Considerations......Page 570 20.4 Spherical Micelles......Page 572 20.5 Nonspherical and Cylindrical Micelles......Page 575 20.6 Bilayers......Page 576 20.7 Vesicles......Page 580 20.8 Curvature/Bending Energies and Elasticities of Monolayers and Bilayers......Page 582 20.9 Other Amphiphilic Structures and the Transitions between Them......Page 590 20.10 Self-Assembly on Surfaces and Interfaces: 2D Micelles, Domains, and Rafts......Page 594 20.12 Membrane Lipids......Page 596 20.13 Membrane Proteins and Membrane Structure......Page 599 Problems And Discussion Topics......Page 601 21.1 Van der Waals Forces......Page 609 21.2 Electrostatic (Double-Layer) and DLVO Forces......Page 611 21.3 Repulsive Entropic (Thermal Fluctuation, Steric-Hydration) Forces: Protrusion, Headgroup Overlap, and Undulation Forces......Page 617 21.4 Attractive Depletion Forces......Page 625 21.5 Attractive Hydrophobic Forces......Page 627 21.6 Biospecificity: Complementary, Site-Specific and Ligand-Receptor (LR) Interactions......Page 631 21.7 Bridging (Tethering) Forces......Page 635 21.8 Interdependence of Intermembrane and Intramembrane Forces......Page 637 21.9 Biomembrane Adhesion, Bioadhesion......Page 639 21.10 Membrane Fusion......Page 643 Problems And Discussion Topics......Page 645 22.2 Interactions that Evolve in Space and Time: Some General Considerations......Page 649 22.3 Biological Rupture and Capture: The Bell and Jarzynski Equations......Page 651 22.4 Multiple Bonds in Series and in Parallel......Page 654 22.6 Dynamic Interactions between Biological Membranes and Biosurfaces......Page 658 22.7 Self-Assembly versus Directed Assembly: Dynamic Phases and Tunable Materials......Page 660 22.8 Motor Proteins, Transport Proteins, and Protein Engines......Page 662 Problems And Discussion Topics......Page 663 References......Page 667 Index......Page 693