Preface to the Third Edition ................................. xvii
Preface to the Second Edition ................................. xix
Preface to the First Edition .................................. xxi
PART ONE. THE FORCES BETWEEN ATOMS AND MOLECULES ................ 1
1 Historical Perspective ....................................... 3
1.1 The Four Forces of Nature ............................... 3
1.2 Greek and Medieval Notions of Intermolecular Forces ..... 3
1.3 The Seventeenth Century: First Scientific Period ........ 5
1.4 The Eighteenth Century: Confusion, Contradictions,
and Controversy ......................................... 7
1.5 The Nineteenth Century: Continuum versus Molecular
Theories ................................................ 8
1.6 Intermolecular Force-Laws and Interaction Potentials:
Long- and Short-Range Forces ............................ 9
1.7 First Successful Phenomenological Theories ............. 12
1.8 First Estimates of Molecular Sizes ..................... 15
1.9 The Twentieth Century: Understanding Simple Systems .... 16
1.10 Recent Trends .......................................... 17
Problems and Discussion Topics .............................. 18
2 Thermodynamic and Statistical Aspects of Intermolecular
Forces ...................................................... 23
2.1 The Interaction of Molecules in Free Space and in
a Medium ............................................... 23
2.2 Self-Energy and Pair Potential ......................... 25
2.3 The Boltzmann Distribution and the Chemical
Potential .............................................. 26
2.1 The Distribution of Molecules and Particles in
Systems at Equilibrium ................................. 27
2.5 The Van der Waals Equation of State (EOS) .............. 30
2.6 The Criterion of the Thermal Energy kT for Gauging
the Strength of an Interaction ......................... 31
2.7 Classification of Forces and Pair Potentials ........... 34
2.8 Theoretical Analyses of Multimolecular Systems:
Continuum and Molecular Approaches ..................... 35
2.9 Molecular Approaches via Computer Simulations:
Monte Carlo (MC) and Molecular Dynamics (MD) ........... 37
2.10 Newton's Laws Applied to Two-Body Collisions ........... 39
2.11 Kinetic and Statistical Aspects of Multiple
Collisions: the Boltzmann Distribution ................. 43
Problems and Discussion Topics .............................. 49
3 Strong Intermolecular Forces: Covalent and Coulomb
Interactions ................................................ 53
3.1 Covalent or Chemical Bonding Forces .................... 53
3.2 Physical and Chemical Bonds ............................ 54
3.3 Coulomb Forces or Charge-Charge Interactions,
Gauss's Law ............................................ 55
3.4 Ionic Crystals ......................................... 58
3.5 Reference States ....................................... 59
3.6 Range of Electrostatic Forces .......................... 60
3.7 The Born Energy of an Ion .............................. 61
3.8 Solubility of Ions in Different Solvents ............... 62
3.9 Specific Ion-Solvent Effects: Continuum Approach ....... 66
3.10 Molecular Approach: Computer Simulations and Integral
Equations of Many-Body Systems ......................... 67
Problems and Discussion Topics .............................. 68
4 Interactions Involving Polar Molecules ...................... 71
4.1 What Are Polar Molecules? .............................. 71
4.2 Dipole Self-Energy ..................................... 73
4.3 Ion-Dipole Interactions ................................ 73
4.4 Ions in Polar Solvents ................................. 78
4.5 Strong Ion-Dipole Interactions in Water: Hydrated
Ions ................................................... 78
4.6 Solvation Forces, Structural Forces, and Hydration
Forces ................................................. 80
4.7 Dipole-Dipole Interactions ............................. 81
4.8 Magnetic Dipoles ....................................... 83
4.9 Hydrogen Bonds ......................................... 83
4.10 Rotating Dipoles and Angle-Averaged Potentials ......... 84
4.11 Entropic Effects ....................................... 86
Problems and Discussion Topics .............................. 88
5 Interactions Involving the Polarization of Molecules ........ 91
5.1 The Polarizability of Atoms and Molecules .............. 91
5.2 The Polarizability of Polar Molecules .................. 93
5.3 Other Polarization Mechanisms and the Effects
of Polarization on Electrostatic Interactions .......... 94
5.4 Interactions between Ions and Uncharged Molecules ...... 96
5.5 Ion-Solvent Molecule Interactions and the Born
Energy ................................................. 98
5.6 Dipole-Induced Dipole Interactions ..................... 99
5.7 Unification of Polarization Interactions ............... 99
5.8 Solvent Effects and "Excess Polarizabilities" ......... 100
Problems and Discussion Topics ............................. 105
6 Van der Waals Forces ....................................... 107
6.1 Origin of the Van der Waals-dispersion Force between
Neutral Molecules: the London Equation ................ 107
6.2 Strength of Dispersion Forces: Van der Waals
Solids and Liquids .................................... 109
6.3 Van der Waals Equation of State ....................... 113
6.4 Gas-Liquid and Liquid-Solid Phase Transitions in 3D
and 2D ................................................ 115
6.5 Van der Waals Forces between Polar Molecules .......... 117
6.6 General Theory of Van der Waals Forces between
Molecules ............................................. 119
6.7 Van der Waals Forces in a Medium ...................... 122
6.8 Dispersion Self-Energy of a Molecule in a Medium ...... 126
6.9 Further Aspects of Van der Waals Forces: Anisotropy
(Orientation), Nonadditivity (Many-Body), and
Retardation Effects ................................... 127
Problems and Discussion Topics ............................. 130
7 Repulsive Steric Forces, Total Intermolecular Pair
Potentials, and Liquid Structure ........................... 133
7.1 Sizes of Atoms, Molecules, and Ions ................... 133
7.2 Repulsive Potentials .................................. 136
7.3 Total Intermolecular Pair Potentials: Their Form,
Magnitude, and Range .................................. 136
7.4 Role of Repulsive Forces in Noncovalently Bonded
Solids ................................................ 140
7.5 Packing of Molecules and Particles in Solids .......... 142
7.6 Role of Repulsive Forces in Liquids: Liquid
Structure ............................................. 145
7.7 The Effect of Liquid Structure on Molecular Forces .... 147
Problems and Discussion Topics ............................. 148
8 Special Interactions: Hydrogen-Bonding and Hydrophobic
and Hydrophilic Interactions ............................... 151
8.1 The Unique Properties of Water ........................ 151
8.2 The Hydrogen Bond ..................................... 152
8.3 Models of Water and Associated Liquids ................ 156
8.4 Relative Strengths of Different Types of
Interactions .......................................... 157
8.5 The Hydrophobic Effect ................................ 158
8.6 The Hydrophobic Interaction ........................... 161
8.7 Hydrophilic Interactions .............................. 163
Problems and Discussion Topics ............................. 166
9 Nonequilibrium and Time-Dependent Interactions ............. 169
9.1 Time- and Rate-Dependent Interactions and Processes ... 169
9.2 Rate- and Time-Depended Detachment (Debonding)
Forces ................................................ 171
9.3 Energy Transfer (Dissipation) during Molecular
Collisions: the Deborah Number ........................ 175
9.4 Energy Transfer during Cyclic Bonding-Unbonding
Processes ............................................. 178
9.5 Relationships between Time, Temperature, and
Velocity (Rate) in Complex Processes .................. 182
Problems and Discussion Topics ............................. 185
PART TWO. THE FORCES BETWEEN PARTICLES AND SURFACES ........... 189
10 Unifying Concepts in Intermolecular and Interparticle
Forces ..................................................... 191
10.1 The Association of Like Molecules or Particles in
a Medium .............................................. 191
10.2 Two Like Surfaces Coming Together in a Medium:
Surface and Interfacial Energy ........................ 196
10.3 The Association of Unlike Molecules, Particles, or
Surfaces in a Third Medium ............................ 197
10.4 Particle-Surface and Particle-Interface
Interactions .......................................... 198
10.5 Engulfing and Ejection ................................ 200
10.6 Adsorbed Surface Films: Wetting and Nonwetting ........ 201
Problems and Discussion Topics ............................. 203
11 Contrasts between Intermolecular, Interparticle,
and Intersurface Forces .................................... 205
11.1 Short-Range and Long-Range Effects of a Force:
Qualitative Differences in the Interactions of
Particles and Small Molecules ......................... 205
11.2 Interaction Potentials between Macroscopic Bodies ..... 208
11.3 Effective Interaction Area of Two Spheres:
the Langbein Approximation ............................ 211
11.4 Interactions of Particles Compared to Those between
Atoms or Small Molecules .............................. 212
11.5 Interaction Energies and Interaction Forces:
the Derjaguin Approximation ........................... 215
11.6 "Body Forces" and "Surface Forces" .................... 220
Problems and Discussion Topics ............................. 220
12 Force-Measuring Techniques ................................. 223
12.1 Direct and Indirect Measurements of Intermolecular,
Interparticle, and Surface Forces ..................... 223
12.2 Different Direct Force-Measuring Techniques ........... 227
12.3 Mechanics of Direct Force Measurements and Problems
of Interpretation ..................................... 231
12.4 Measuring Force-Distance Functions, F(D) .............. 234
12.5 Instabilities ......................................... 235
12.6 Measuring Adhesion Forces and Energies ................ 237
12.7 Measuring Forces between Macroscopic Surfaces:
the SFA, OP /OS and Related Techniques ................ 239
12.8 Measuring Forces between Microscopic (Colloidal)
and Nanoscopic Particles: AFM and TIRM Techniques ..... 245
12.9 Measuring Single-Molecule and Single-Bond
Interactions: ОТ and MC Techniques .................... 248
Problems and Discussion Topics ............................. 250
13 Van der Waals Forces between Particles and Surfaces ........ 253
13.1 Van der Waals Force-Laws for Bodies of Different
Geometries: the Hamaker Constant ...................... 253
13.2 Strength of Van der Waals Forces between Bodies in a
Vacuum or Air ......................................... 255
13.3 The Lifshitz Theory of Van der Waals Forces ........... 256
13.4 Particle-Surface Interactions ......................... 259
13.5 Nonretarded Hamaker Constants Calculated on the
Basis of the Lifshitz Theory .......................... 260
13.6 Van der Waals Forces between Conducting Media ......... 261
13.7 Theoretical and Experimental Hamaker Constants
for Interactions in a Vacuum or Air ................... 263
13.8 Applications of the Lifshitz Theory to Interactions
in a Medium ........................................... 264
13.9 Repulsive Van der Waals Forces: Disjoining Pressure
and Wetting Films ..................................... 267
13.10 Van der Waals Forces at Large Separations:
Retardation Effects .................................. 270
13.11 Electrostatic Screening Effects in Electrolyte
Solutions ............................................ 274
13.12 Combining Relations .................................. 274
13.13 Surface and Adhesion Energies ........................ 275
13.14 Surface Energies of Metals ........................... 280
13.15 Forces between Surfaces with Adsorbed Layers ......... 281
13.16 Experiments on Van der Waals Forces .................. 282
Problems and Discussion Topics ............................. 284
14 Electrostatic Forces between Surfaces in Liquids ........... 291
14.1 The Charging of Surfaces in Liquids: the Electric
"Double-Layer" ........................................ 291
14.2 Charged Surfaces in Water: No Added Electrolyte—
"Counterions Only" .................................... 293
14.3 The Poisson-Boltzmann (PB) Equation ................... 293
14.4 Surface Charge, Electric Field, and Counterion
Concentration at a Surface: "Contact" Values .......... 294
14.5 Counterion Concentration Profile Away from
a Surface ............................................. 296
14.6 Origin of the Ionic Distribution, Electric Field,
Surface Potential, and Pressure ....................... 298
14.7 The Pressure between Two Charged Surfaces in Water:
the Contact Value Theorem ............................. 300
14.8 Limit of Large Separations: Thick Wetting Films ....... 303
14.9 Limit of Small Separations: Osmotic Limit and Charge
Regulation ............................................ 305
14.10 Charged Surfaces in Electrolyte Solutions ............ 306
14.11 The Grahame Equation ................................. 308
14.12 Surface Charge and Potential of Isolated Surfaces .... 309
14.13 Effect of Divalent Ions .............................. 311
14.14 The Debye Length ..................................... 312
14.15 Variation of Potential ψx and Ionic Concentrations
px Away from a Surface ............................... 313
14.16 Electrostatic Double-Layer Interaction Forces and
Energies between Various Particle Surfaces ........... 314
14.17 Exact Solutions for Constant Charge and Constant
Potential Interactions: Charge Regulation ............ 318
14.18 Asymmetric Surfaces .................................. 321
14.19 Ion-Condensation and Ion-Correlation Forces .......... 322
14.20 More Complex Systems: Finite Reservoir Systems and
Finite Ion-Size Effects .............................. 325
14.21 Van der Waals and Double-Layer Forces Acting
Together: the DLVO Theory ............................ 326
14.22 Experimental Measurements of Double-Layer and DLVO
Forces ............................................... 331
14.23 Electrokinetic Forces ................................ 334
14.24 Discrete Surface Charges and Dipoles ................. 335
Problems and Discussion Topics ............................. 338
15 Solvation, Structural, and Hydration Forces ................ 341
15.1 Non-DLVO Forces ....................................... 341
15.2 Molecular Ordering at Surfaces, Interfaces, and in
Thin Films ............................................ 342
15.3 Ordering of Spherical Molecules between Two Smooth
(Unstructured) Surfaces ............................... 345
15.4 Ordering of Nonspherical Molecules between
Structured Surfaces ................................... 347
15.5 Origin of Main Type of Solvation Force: the
Oscillatory Force ..................................... 349
15.6 Jamming ............................................... 354
15.7 Experimental Measurements and Properties of
Oscillatory Forces .................................... 355
15.8 Solvation Forces in Aqueous Systems: Monotonically
Repulsive "Hydration" Forces .......................... 361
15.9 Solvation Forces in Aqueous Systems: Attractive
"Hydrophobic" Forces .................................. 370
Problems and Discussion Topics ............................. 378
16 Steric (Polymer-Mediated) and Thermal Fluctuation Forces ... 381
16.1 Diffuse Interfaces in Liquids ......................... 381
16.2 The States of Polymers in Solution and at Surfaces .... 381
16.3 Repulsive "Steric" or "Overlap" Forces between
Polymer-Covered Surfaces .............................. 387
16.4 Interparticle Forces in Pure Polymer Liquids
(Polymer Melts) ....................................... 393
16.5 Attractive "Intersegment" and "Bridging" Forces ....... 394
16.6 Attractive "Depletion" Forces ......................... 398
16.7 Polyelectrolytes ...................................... 402
16.8 Nonequilibrium Aspects of Polymer Interactions ........ 404
16.9 Thermal Fluctuations of and Forces between
Fluid-Like Interfaces ...................................... 405
16.10 Short-Range Protrusion Forces ........................ 406
16.11 Long-Range Undulation Forces ......................... 408
Problems and Discussion Topics ............................. 411
17 Adhesion and Wetting Phenomena ............................. 415
17.1 Surface and Interfacial Energies ...................... 415
17.2 Adhesion Energies versus Adhesion Forces .............. 419
17.3 Highly Curved Surfaces and Interfaces: Clusters,
Cavities, and Nanoparticles ........................... 422
17.4 Contact Angles and Wetting Films ...................... 429
17.5 Wetting of Rough, Textured, and Chemically
Heterogeneous Surfaces ................................ 434
17.6 Contact Angle Hysteresis .............................. 439
17.7 Adhesion of Solid Particles: the JKR and Hertz
Theories .............................................. 442
17.8 Adhesion Hysteresis ................................... 448
17.9 Adhesion of Rough and Textured Surfaces ............... 452
17.10 Plastic Deformations ................................. 453
17.11 Capillary Forces ..................................... 456
Problems and Discussion Topics ............................. 461
18 Friction and Lubrication Forces ............................ 469
18.1 Origin of Friction and Lubrication Forces ............. 469
18.2 Relationship between Adhesion and Friction Forces ..... 476
18.3 Amontons' Laws of (Dry) Friction ...................... 481
18.4 Smooth and Stick-Slip Sliding ......................... 482
18.5 Lubricated Sliding .................................... 485
18.6 Transitions between Liquid- and Solid-Like Films ...... 490
18.7 The "Real" Area of Contact of Rough Surfaces .......... 493
18.8 Rolling Friction ...................................... 494
18.9 Theoretical Modeling of Friction Mechanisms ........... 495
Problems and Discussion Topics ............................. 497
PART THREE. SELF-ASSEMBLING STRUCTURES AND BIOLOGICAL
SYSTEMS ....................................................... 501
19 Thermodynamic Principles of Self-Assembly .................. 503
19.1 Introduction: Soft Structures ......................... 503
19.2 Fundamental Thermodynamic Equations of Self-
Assembly .............................................. 504
19.3 Conditions Necessary for the Formation of
Aggregates ............................................ 509
19.4 Effect of Dimensionality and Geometry: Rods,
Discs, and Spheres .................................... 510
19.5 The Critical Micelle Concentration (CMC) .............. 512
19.6 Infinite Aggregates (Phase Separation) versus Finite
Sized Aggregates (Micellization) ...................... 513
19.7 Hydrophobic Energy of Transfer ........................ 514
19.8 Nucleation and Growth of Aggregates ................... 515
19.9 2D Structures on Surfaces: Soluble and Insoluble
Monolayers ............................................ 520
19.10 Line Tension and 2D Micelles (Domains) ............... 521
19.11 Soluble Monolayers and the Gibbs Adsorption
Isotherm ............................................. 524
19.12 Size Distributions of Self-Assembled Structures ...... 524
19.13 Large and More Complex Amphiphilic Structures ........ 527
19.14 Effects of Interactions between Aggregates:
Mesophases and Multilayers ........................... 528
Problems and Discussion Topics ............................. 530
20 Soft and Biological Structures ............................. 535
20.1 Introduction: Equilibrium Considerations of Fluid
Amphiphilic Structures ................................ 535
20.2 Optimal Headgroup Area ................................ 536
20.3 Geometric Packing Considerations ...................... 538
20.4 Spherical Micelles .................................... 540
20.5 Nonspherical and Cylindrical Micelles ................. 543
20.6 Bilayers .............................................. 544
20.7 Vesicles .............................................. 548
20.8 Curvature/Bending Energies and Elasticities of
Monolayers and Bilayers ............................... 550
20.9 Other Amphiphilic Structures and the Transitions
between Them .......................................... 558
20.10 Self/Assembly on Surfaces and Interfaces: 2D
Micelles, Domains, and Rafts .......................... 562
20.11 Biological Membranes ................................. 564
20.12 Membrane Lipids ...................................... 564
20.13 Membrane Proteins and Membrane Structure ............. 567
Problems and Discussion Topics ............................. 569
21 Interactions of Biological Membranes and Structures .... 577
21.1 Van der Waals Forces .................................. 577
21.2 Electrostatic (Double-Layer) and DLVO Forces .......... 579
21.3 Repulsive Entropic (Thermal Fluctuation, Steric-
Hydration) Forces: Protrusion, Headgroup Overlap,
and Undulation Forces ................................. 585
21.4 Attractive Depletion Forces ........................... 593
21.5 Attractive Hydrophobic Forces ......................... 595
21.6 Biospecificity: Complementary, Site-Specific
and Ligand-Receptor (LR) Interactions ................. 599
21.7 Bridging (Tethering) Forces ........................... 603
21.8 Interdependence of Intermembrane and Intramembrane
Forces ................................................ 605
21.9 Biomembrane Adhesion, Bioadhesion ..................... 607
21.10 Membrane Fusion ...................................... 611
Problems and Discussion Topics ............................. 613
22 Dynamic Biointeractions .................................... 617
22.1 Subtleties of Biological Forces and Interactions ...... 617
22.2 Interactions that Evolve in Space and Time: Some
General Considerations ................................ 617
22.3 Biological Rupture and Capture: The Bell and
Jarzynski Equations ................................... 619
22.4 Multiple Bonds in Series and in Parallel .............. 622
22.5 Detachment versus Capture Processes: Biological
Importance of "Rare Events" ........................... 626
22.6 Dynamic Interactions between Biological Membranes
and Biosurfaces ....................................... 626
22.7 Self-Assembly versus Directed Assembly: Dynamic
Phases and Tunable Materials .......................... 628
22.8 Motor Proteins, Transport Proteins, and Protein
Engines ............................................... 630
Problems and Discussion Topics ............................. 631
References .................................................... 635
Index ......................................................... 661
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