Intermolecular and surface forces

Fundamental Constants\n......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 -\nThe 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 -\nThe 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:\nQualitative Differences in the Interactions\nof 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 -\nSelf-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