Contents

PART ONE
The Forces Between Atoms and Molecules:
Principles and Concepts
Chapter 1 Historical Perspective 3
1.1 The four forces of nature 3
1.2 Creek and medieval notions of intermolecular forces 3
1.3 Early scientific period: contrasts with gravitational forces 5
1.4 First successful phenomenological theories 8
1.5 Modern view of the origin of intermolecular forces 11
1.6 Recent trends 11
Problems and discussion topics

Chapter 2 Some Thermodynamic Aspects of Intermolecular 16

Forces

2.1 Interaction energies of molecules in free space and in a 16

medium
2.2 The Boltzmann distribution 20
2.3 The distribution of molecules and particles in systems at 21
equilibrium
2.4 The van der Waals equation of state 23
2.5 The criterion of the thermal energy kl for gauging the 24
strength of an interaction
2.6 Classification of forces 27
Problems and discussion topics

Chapter 3 Strong Intermolecular Forces: Covalent and Coulomb 31

Interactions

3.1 Covalent or chemical bonding forces 31

3.2 Physical and chemical bonds 32
 CONTENTS

3.3 Coulomb forces or charge-charge interactions 32

3.4 Ionic crystals 35
3.5 Reference states 36
3.6 Range of Coulomb forces 36
3.7 The Born energy of an ion 37
3.8 Solubility of ions in different solvents 38
3.9 Specific ion-solvent effects 42
3.10 Continuum approach 43
3.11 Molecular approach: computer simulations 44
Problems and discussion topics

Chapter 4 Interactions Involving Polar Molecules 48

4.1 What are polar molecules? 48

4.2 Dipole self-energy 50
4.3 lon-dipole interactions 50
4.4 Ions in polar solvents 54
4.5 Strong ion-dipole interactions: hydrated ions 55
4.6 Solvation forces, structural forces, hydration forces 56
4.7 Dipole-dipole interactions 57
4.8 Rotating dipoles and angle-averaged potentials 60
4.9 Entropic effects 63
Problems and discussion topics

Chapter 5 Interactions Involving the Polarization of Molecules 67

5.1 The polarizability of atoms and molecules 67

5.2 The polarizability of polar molecules 70
5.3 Interactions between ions and uncharged molecules 71
5.4 Ion-solvent molecule interactions and the Born energy 73
5.5 Dipole-induced dipole interactions 74
5.6 Unification of polarization interactions 75
5.7 Solvent effects and 'excess polarizabilities' 76
Problems and discussion topics

Chapter 6 van der Waals Forces 83

6.1 Origin of the van der Waals dispersion force between 83

neutral molecules: the London equation
6.2 Strength of dispersion forces: van der Waals solids and 85
liquids
6.3 van der Waals equation of state 90
6.4 Gas-liquid and liquid-solid phase transitions 91
6.5 van der Waals forces between polar molecules 93
6.6 General theory of van der Waals forces between molecules 96
 CONTENTS VII

6.7 van der Waals forces in a medium 99

6.8 Dispersion self-energy of a molecule in a medium 103
6.9 Further aspects of van der Waals forces: anisotropy, non- 105
additivity and retardation effects
Problems and discussion topics

Chapter 7 Repulsive Forces, Total Intermolecular Pair Potentials 109

and Liquid Structure

7.1 Sizes of atoms, molecules and ions 109

7.2 Repulsive potentials 112
7.3 Total intermolecular pair potentials 113
7.4 Role of repulsive forces in non-covalently bonded solids 115
7.5 Role of repulsive forces in liquids: liquid structure 117
7.6 Effect of liquid structure on molecular forces 119
Problems and discussion topics

Chapter 8 Special Interactions: Hydrogen-Bonding, 122

Hydrophobic and Hydrophilic Interactions

8.1 The unique properties of water 122

8.2 The hydrogen bone) 123
8.3 Models of water and associated liquids 125
8.4 Relative strengths of different types of interactions 127
8.5 The hydrophobic effect 128
8.6 The hydrophobic interaction 131
8.7 Hydrophilicity 133
Problems and discussion topics

PART TWO
The Forces Between Particles and Surfaces
Chapter 9 Some Unifying Concepts in Intermolecular and 139
Interparticle Forces
9.1 Factors favouring the association of like molecules or 139
particles in a medium
9.2 Two like surfaces coming together in a medium: surface 144
and interfacial energy
9.3 Factors favouring the association of unlike molecules, 145
particles or surfaces in a third medium
9.4 Particle-surface interactions 147
VIII CONTENTS

9.5 Adsorbed surface films: wetting and non-wetting 149

Problems and discussion topics

Chapter 10 Contrasts Between Intermolecular, Interparticle and 152

Intersurface Forces

10.1 Short-range and long-range effects of a force 152

10.2 Interaction potentials between macroscopic bodies 155
10.3 Effective interaction area of two spheres: the Langbein 159
approximation
10.4 Interactions of large bodies compared to those between 159
molecules
10.5 Interaction energies and interaction forces: the Derjaguin 161
approximation
10.6 Experimental measurements of intermolecular and surface 165
forces
10.7 Direct measurements of surface and intermolecular forces 168
Problems and discussion topics

Chapter 11 van der Waals Forces Between Surfaces 176

11.1 The force laws for bodies of different geometries: the 176
Hamaker constant
11.2 Strength of van der Waals forces between bodies in 178
vacuum or air
11.3 The Lifshitz theory of van der Waals forces 179
11.4 Hamaker constants calculated on the basis of the Lifshitz 183
theory
11.5 Applications of the Lifshitz theory to interactions in a 188
medium
11.6 Repulsive van der Waals forces: disjoining pressure and 192
wetting films
11.7 Retardation effects 196
11.8 Screened van der Waals forces in electrolyte solutions 199
11.9 Combining relations 200
11.10 Surface and adhesion energies 201
11.11 Surface energies of metals 204
11.12 Forces between surfaces with adsorbed layers 206
11.13 Experiments on van der Waals forces 207
Problems and discussion topics

Chapter 12 Electrostatic Forces Between Surfaces in Liquids 213

12.1 The charging of surfaces in liquids: the electric 'double 213

layer'
 CONTENTS IX

12.2 Charged surfaces in water (no added electrolyte) 215

12.3 The Poisson-Boltzmann (PB) equation 215
12.4 Surface charge, electric field and counterion concentration 217
at a surface
12.5 Counterion concentration profile away from a surface 219
12.6 Origin of the ionic distribution, electric field, surface potential 221
and pressure
12.7 The pressure between two charged surfaces in water: the 223
contact value theorem
12.8 Limitations of the Poisson-Boltzmann equation 227
12.9 Thick wetting films 229
12.10 Limit of small separations: charge regulation 230
12.11 Charged surfaces in electrolyte solutions 231
12.12 The Grahame equation 233
12.13 Surface charge and potential in the presence of monovalent 234
ions
12.14 Effect of divalent ions 237
12.15 The Debye length 238
12.16 Variation of potential and ionic concentrations away from 239
a charged surface
12.17 The electrostatic double-layer interaction between charged 241
surfaces in electrolyte
12.18 van der Waals and double-layer forces acting together: 246
the DLVO theory
12.19 Experimental measurements of double-layer and DLVO 250
forces
12.20 Effects of discrete surface charges and dipoles 254
Problems and discussion topics

Chapter 13 Solvation, Structural and Hydration Forces 260

13.1 Non-DLVO forces 260

13.2 Molecular ordering at surfaces and interfaces and in thin 261
films
13.3 Origin of main type of solvation force: the oscillatory force 265
13.4 Measurements and properties of solvation forces: oscillatory 269
forces in non-aqueous liquids
13.5 Solvation forces in aqueous systems: repulsive 'hydration' 275
forces
13.6 Solvation forces in aqueous systems: attractive 'hydro- 282
phobic' forces
Problems and discussion topics

Chapter 14 Steric and Fluctutation Forces 288

14.1 Diffuse interfaces 288

14.2 Polymers at surfaces 289
X CONTENTS

14.3 Repulsive 'steric' or 'overlap' forces between polymer- 293

covered surfaces
14.4 Forces in pure polymer liquids (polymer melts) 298
14.5 Attractive 'intersegment,' 'bridging' and 'depletion' forces 299
14.6 Non-equilibrium aspects of polymer interactions 303
14.7 Thermal fluctuation forces between fluid-like surfaces 304
14.8 Protrusion forces 304
14.9 Undulation and peristaltic forces 307
Problems and discussion topics

Chapter 15 Adhesion 312

15.1 Surface and interfacial energies 312

15.2 Surface energies of small clusters and highly curved surfaces 317
15.3 Contact angles and wetting films 319
15.4 Hysteresis in contact angle and adhesion measurements 322
15.5 Adhesion force between solid particles: the JKR and Hertz 326
theories
15.6 Effect of capillary condensation on adhesion 330
Problems and discussion topics

PART THREE
Fluid-Like Structures and Self-Assembling Systems:
Micelles, Bilayers and Biological Membranes
Chapter 16 Thermodynamic Principles of Self-Assembly 341
16.1 Introduction 341
16.2 Fundamental thermodynamic equations of self-assembly 345
16.3 Conditions necessary for the formation of aggregates 348
16.4 Variation of n% with N for simple structures of different 349
geometries: rods, discs and spheres
16.5 The critical micelle concentration (CMC) 351
16.6 Infinite aggregates (phase separation) versus finite-sized 352
aggregates (micellization)
16.7 Size distributions of self-assembled structures 354
16.8 More complex amphiphilic structures 360
16.9 Effects of interactions between aggregates: mesophases and 362
multilayers
16.10 Conclusion 364
Problems and discussion topics
 CONTENTS XI

Chapter 17 Aggregation of Amphophilic Molecules into Micelles, 366

Bilayers, Vesicles and Biological Membranes

17.1 Introduction: equilibrium considerations of amphiphilic 366

structures
17.2 Optimal headgroup area 367
17.3 Geometric packing considerations 370
17.4 Spherical micelles 371
17.5 Non-spherical and cylindrical micelles 374
17.6 Bilayers 375
17.7 Vesicles 378
17.8 Factors affecting changes from one structure to another 380
17.9 Curvature elasticity of bilayers and membranes 382
17.10 Biological membranes 385
17.11 Membrane lipids 387
17.12 Membrane proteins and membrane structure 389
Problems and discussion topics

Chapter 18 The Interactions between Lipid Bilayers and Biological 395

Membranes

18.1 Introduction 395

18.2 Attractive van der Waals forces 395
18.3 Electrostatic (double-layer) forces 396
18.4 Hydration forces 399
18.5 Limitations of the hydration model 402
18.6 Steric forces 405
18.7 Hydrophobic forces 408
18.8 Specific interactions 410
18.9 Interdependence of intermembrane and intramembrane 412
forces
18.10 Adhesion 414
18.11 Fusion 416
Problems and discussion topics

References 422
Index 437
LIST OF TABLES

Page
Table 2.1 Boiling points and latent heats (Trouton's rule) 26
Table 3.1 Strengths of covalent bonds 32
Table 3.2 Dielectric constants of solids and liquids 41
Table 4.1 Dipole moments of molecules and molecular groups 49
Table 4.2 Hydrated radii of ions 55
Table 5.1 Polarizabilities of atoms and molecules 609
Table 5.2 Molecular polarizabilities from molecular and bulk 80
properties
Table 6.1 Van der Waals dispersion interaction between non-polar 87
molecules
Table 6.2 Van der Waals dispersion interaction between alkane 89
molecules
Table 6.3 Van der Waals interaction between polar molecules 95
Table 7.1 Molecular radii deduced from different methods 111
Table 7.2 Effects of hydrocarbon chain unsaturation and branching 116
on melting points
Table 8.1 Relative strengths of dispersion, dipolar and H-bonding 128
interactions
Table 8.2 Hydrophilic groups and surfaces 134
Table 11.1 Hamaker constants determined from pairwise additivity 178
Table 11.2 Hamaker constants across a vacuum 186
Table 11.3 Hamaker constants across a medium 190
Table 11.4 Surface energies (tensions) calculated from Lifshitz theory 204
Table 11.5 Surface energies of metals (experimental) 205
Table 11.6 Surface energies of metals (calculated) 206
Table 12.1 Surface potentials in different electrolyte solutions 235
Table 14.1 Common polymers 290
Table 15.1 Interfacial energies (tensions) 315
Table 15.2 Relation between surface tension and detergent action 337
Table 16.1 Common amphiphiles 342

XII
 LIST OF TABLES

Table 16.2 Critical micelle concentrations 355

Table 17.1 Chain melting temperatures of lipid bilayers 378
Table 17.2 Common amphiphilic structures 381

Addivity, 180, 188, 267
of van der Waals forces, 89, 106,
177-179, 202
Adhesion
and surface energy, 163, 267, 270,
334, 336-337
Mayer, 309, 397, 414-416, 421
effect of adsorbed layers, 207
effect of capillary forces, 330-333,335
effect of meniscus, 330-333, 335
effect of solvation force, 267-270
effect of surface asperities, 323,329,333
effect of surface roughness, 329, 333
effect of tension, 309
effect of water, 210, 271, 333, 336
energy, 144, 163, 179, 201-204, 210,
267-268, 270, 312-313
force, 9-10, 163, 172, 210, 267, 270,
327, 328, 414-416
hysteresis, 322-323
measurement, 165-168, 172, 270, 333,
415
mechanics, 326-329
membrane, 397, 414-416, 421
of deformable surfaces, 326, 414-416
of elastic bodies, 326-327, 336-337,
414-416
specific, 410-412
theoretical aspects, 9-10, 163,
267-268, 334, 414-416
vesicle, 414-416
work of, 313
Adsorbed film, 149-151, 195, 198, 206,
210
effect on adhesion, 207, 323
effect on contact angle, 322-323
liquid helium, 192-194
436
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non-wetting, 284
of liquid, 192-195, 198, 210
theoretical aspects, 149-151, 192-195
Adsorption on surfaces, 147-151, 195,
206, 236
Aging effects, 303
Aggregates, see Amphiphilic structures,
Micelle, Self-assembly
Alder transition, 93
Amphiphilic molecules, 135, 342-343
biological, 342-343, 387
critical chain length, 370
exchange, 346, 375
forces between, 361, 341
in biological membranes, 342-343
lifetime in micelle, 346, 375-376
lifetimes in aggregates, 346, 375
melting temperatures, 378
optimal area, 368-370
packing of, 370
pK values, 342
self-assembly of, 345
structure, 344
unsaturated, 342-343, 387
Amphiphilic structures, 344, 346, 371,
380-381; see also Aggregates
bicontinuous, 392
effect of temperature, 380-382
effect of two chains, 375
forces between, 276, 395, 414-416
inverted, 379, 392, 420
periodic, 392
phase equilibrium, 367
phase transisions, 353
polydispersity, 358-362,373-374,385
size distribution, 354-362, 373-374,
385
 INDEX 437

transitions between, 380-382, structure, 344, 376

362-364, 392 Bilayer-vesicle transition, 364
Amphoteric surfaces, 236-238; 280 Biocontinuous structures, 392
Angle-averaged potential, 60, 61, 66, 74 Biological membrane, 385-392
Anisotropic interaction, see Orientation composition, 386
dependent interaction fusion, 409, 416-419
Archimedes' principle, 145 in cells, 386
Area interactions, 413
effective, for spheres, 143, 174 properties, 389
of contact, 143 structure, 390-394, 413
of headgroups, 380 Bohr atom, 84, 88, 179
of interaction, 143, 159, 174 Bohr radius, 84
Association Boiling temperature
of molecules and particles, 133, and intermolecular forces, 25-27, 87,
139-142, 145-146, 151 115-116
Associated liquid, 26, 59-60, 125-127, Boltzmann-averaged potential, 6 0 - 6 2
268 Boltzmann distribution, 20-22, 27, 119,
Association of molecules, 133, 139, 141, 215
142 of ions, 231-233
Association of particles, 141, 142, 145 Boltzmann factor, 20-22, 27
Atmosphere Boltzmann statistics, 23
earth's, 21 Bond
ionic, see Double-layer chemical, 31
Atomic Force Microscopy (AFM), 10, covalent, 31-32
14, 15, 173 directionality of, 31-32
Atomic size, 110 energy, 19, 32
Atom-surface interaction, 14-15, hydrogen, see Hydrogen bond
155-157, 176-178 ionic, 44, 32-37
length, 110-111
metallic, 3 1 - 3 2
Bare ion radius, 55 moment, 49
Barometric distribution law, 21 physical, 32
Bending modulus, of membrane, 383, polarizability, 69
308-309f382-385 strength, 32
Bernal-Fowler rules, 286 Born energy, 37-38, 42-44, 63-64,
Bilayer, 344, 375-378 73-74
diffusion in, 376 limits of applicability, 7 3 - 7 4
dimensions, 344, 376 Born repulsion, 109-112
elasticity, 308-309, 377, 382-385, 421 Boundary lipids, 389
flip-flop, 376 Bridging force
fluid states of, 37 between biopolymers, 411-42
fluidity of, 383 ionic, 410
forces between, 199, 226-228, 252, of polymers, 297, 299-302, 411-412
256, 257, 276-277, 284-285, Brownian collisions, 47, 154-155
304-309, 311, 395-399, 403-409, Brush, polymer, 291
419 theory of, 295
free and supported, 403 Bubble coalescence, 281
fusion, 409, 416-419
lipid diffusion, 376
lipid dynamics in, 377 Capacitor, 34-35
solute diffusion across, 344 Capillarity, 5 - 8
438 INDEX

Capillary Co-ions, 214

condensation, 330 Colloid, order in, 92-93, 227
effect on adhesion, 330-333 Colloidal stability and instability, 120,
forces, 330, 333 247-250, 253, 257, 280, 287,
rise, of liquids, 5 - 8 , 229 310-311, 333
Carbon, 173 Colloidal particles
Casimir- Polder equation, 108 coagulation, 154-155, 247-250
Cavity D L V O forces between, 247-250
energy, 17, 318 Combining relations, 139, 144, 200
nucleation of, 286, 334 Computer simulation, 44-447, 220-221
Cellular membrane, see Biological of adsorbed polymers, 292
membrane of ions near surface, 220-221,239-240
Chain-melting temperature, 378 of liquids, 265
Chaotropic agent, 135 of solvation forces, 265-266
Charge density, of surfaces, 213-215 Constant charge interaction, 245-246
Charge-dipole interaction, 50-64 Constant potential interaction, 245-246
Charge electroneutrality, 34 Contact angle, 149-151, 319, 321-324,
Charge-fluctuation force, 83 334-335, 412
Charge regulation, 230, 235-236, 243 advancing and receding, 321-324
Charge reversal, 237 hysteresis, 321-324
Chemical bond, 32, 46 low values, 322
Chemical potential, 20 of adhering vesicles, 414-416
in chemical equilibrium, 2 0 - 2 2 theoretical aspects, 149-151, 321, 334
in intermolecular interactions, 2 0 - 2 2 Contact area, 159
in self-assembly, 345 Contact mechanics, 326-329
of gas, 23 Contact value theorem, 11,225,265,308
Chord theorem, 143 Continuum theories, 43
Classification of forces, 11-12, 27-29 limitations of, 4 2 - 4 4
Clathrate, 130 Cooperative interactions, 127, 318
Clausius-Mossotti equation, 79, 82, Co-polymers, 296
102, 123 Correlations, in position, 118
Clays Co-surfactant, 382
forces between, 226-228, 276 Coulomb
hydration effects, 226-227, 276 force, 11, 2 7 - 2 8 , 32-37, 39, 4 3 - 4 4
surfaces of, 276 interaction, 11, 32-39, 43-44, 46, 52,
swelling, 172, 226-227, 279, 281 58, 64, 121, 126
Close packing, 117 law, 33
nonspherical molecules, 115-116 Counterion, 214
of colloidal particles, 9 2 - 9 3 Covalent bond, 31-32
random, 120 Creep, 325
spherical molecules, 9 2 - 9 3 , 120 Critical aggregation concentration
Cluster, 317; see also droplet (CAC), 351-352, 364
Coagulation, 120, 168 Critical coagulation concentration
critical concentration of, 247-248 (CCC), 347-348
rate, 154-155 Critical micelle concentration (CMC),
Cohesion, work of, 313 348, 351-352, 375
Cohesive energy, 18, 26, 143 effects on, 355, 392-393
molar, 25-26, 8 6 - 8 9 increment per C H 2 group, 354-355
of atoms and molecules, 18-20, values for, 355
25-26, 8 6 - 8 9 Critical packing parameter, 371-372
 INDEX 439

Critical point wetting, 151 induced, 67-73, 84

Curvature interactions, 50-64, 128
elastic modulus of, 382-385 lattice, 254-256
of surface, 394 permanent, 4 8 - 4 9
rotating, 8 0 - 8 2
self-energy, 50
surface, 254-256
de Broglie wavelength, 23 Dipole-dipole interaction, 57-66, 128,
Debye unit, 49 256
Debye-Hiickel equation, 239 Dipole moment, 4 8 - 4 9
Debye-Hiickel theory, 239 of bond, 49
Debye-induction interaction, 7 5 - 7 6 , water, 37
9 4 - 9 5 , 182 Directionality
Debye-Langevin equation, 70, 79, 82, of bonds, 127-128
97, 123 of van der Waals force, 89, 115
Debye length, 199, 238, 243 Discrete charge effects, 254-256
in van der Waals force, 199 Disjoining pressure, 192-194, 229
Deformation, during adhesion Dispersion interaction, 8 3 - 8 9 ; see also
of particles, 326-329 van der Waals interaction
of vesicles, 414-416 Distribution function, 19
Density distribution density, 117-118
function, 19, 117-118 radial, 117-118
in liquids, 18-19, 117-119, 261-264 Divalent ion effects, 228
of molecules, 18-19, 261-264 on forces, 257, 397
of polymer layer, 292 on surface charge and potential, 237
Depletion force, 302-303, 310-311 D L V O forces, 246-253, 277
Derjaguin approximation, 161-164, between bilayers, 256, 397-398
172, 175, 243, 270, 326 in colloidal stability, 247-250
Derjaguin-Landau-Verwey-Overbeek in non-aqueous liquids, 273-274
( D L V O ) theory, 246-250; see also measurements, 250-253, 397
D L V O forces D L V O theory, see
limitations, 252-254 Derjaguin-Landau-Verwey-
Desorption-, 147-151 Overbeek theory
Detergent action, 7, 336 Double-layer, 214
Dielectric constant, 29, 41, 44, 7 9 - 8 0 effect on surface energy, 258
limitation, at small distances, 42-44, thickness of, 238
79-82 Double-layer interaction, 223, 241, 401
role, in interactions, 4 2 - 4 4 , 7 9 - 8 1 at constant change, 244-246, 257
temperature-dependence of, 8 0 - 8 1 at constant potential, 242-246
values, 41 between bilayers and membranes,
Dielectric sphere in medium, 7 7 - 8 1 225-226, 257, 396-397, 401
Diffuse double-layer, see Double-layer between planar surfaces, 221-226,
Diffuse interface, 92, 288 245-246, 257
Dipolar interactions, 50-64, 128 charge regulation in, 230,244-246,401
Dipolar ions, 40, 48 computed values for, 245-246
Dipolar molecule, see Polar molecule expressions for, 242-244, 257
Dipole, 27, 48 in thin films, 229
effect on forces, 273 measurement, 225-226, 250-253,
field, 74, 254-256 257, 274, 397, 401
forces between, 256 theory, 223-225, 241-242
440 INDEX

Droplet Entropy, 20, 63

surface energy of, 317-318, 336 configurational, 20
water, 319 effects, 63-64
Dupre equation, 314 excluded volume, 23-24
of association, 133
of confinement, 20
Effective area of interaction, 143,159,175 of dilution, 20
Elasticity, of surface, 175 of mixing, 20
Elasticity, of membranes, 308-309, role, in interactions, 63-64, 129, 259,
382-385 421
Electric dipole, see Dipole Equation
Electric double-layer, see Double-layer Boltzmann distribution, 20-22
Electric field Casimir-Polder, 108
image, 72, 180 Clausius-Mossotti, 79, 82, 102, 123
near a surface, 34-35,47,217-220,239 Coulomb law, 32-39
of charge, 33-35 Debye-Huckel, 239
of dipole, 74 Debye-Langevin, 70, 79, 82, 97, 123
reflected, 72 Derjaguin approximation, 161-164
screened, 37, 199 Dupre, 314
strength, 33-35, 217-218 Gibbs-Helmholtz, 62
Electronic polarizability, 67-70, 74 Grahame, 234
Electric potential, 21, 34-35 Guoy-Chapman, 239
at surface, 220 Kelvin, 331
Electrolyte Langmuir, 229
asymmetrical, 239 Laplace, 195, 331
symmetrical, 239 Lennard-Jones potential, 9, 14, 44,
Electromagnetic force, 3-5, 11 46, 175
Electroneutrality, 34, 217, 222 Lifshitz, 181, 197
Electrostatic energy, 37, 43-44 London, 85, 88, 99, 101, 104, 108,
Electrostatic interaction, 11, 27, 223, 113-114
421; see also Double-layer Lorentz-Lorentz, 79, 102
interaction McLachlan, 96
between ions in solution, 221-223 Mie potential, 8
between surfaces in water, 221-226 Nernst, 21
range, 36-37 Poisson, 215
Electrostatic potential, see electric Poisson-Boltzmann, 215, 219, 222
potential Schrodinger, 11
Energy Young, 150, 321
adhesion, see Work of adhesion Young-Dupre, 150, 321
Born, 37-38, 42-44, 63-64 Equation of state
crystal lattice, 36, 46 two dimensional, 29, 65-66, 91
dissipation, in adhesion, 323, 329 van der Waals, 8, 23-24, 90-91, 112,
of bonds, 19, 32 368
self, 18, 103-105 Equilibrium, 20-21, 153
surface, see surface energy Excess polarizability, 77, 99, 181
thermal, 24-27 Exchange interaction, 29, 109
Engulfing, 147-148, 183 Exchange rate
Entropic effects, 63-64 of lipids, 346, 375-377
in interactions, 129, 259, 421 of water, 55-56
Entropic interactions, 223, 265, 282, Excluded area, 91
288, 302-304, 405-408 Excluded volume, 23-24, 90-93
 INDEX 441

Falling bodies, 13 osmotic, 407

Fermi length, 205 undulation, 403, 407
Field, see also Electric field van der Waals, 114, 169, 172, 197
of charge, 3 3 - 3 6 Fusion, 416-419
of dipole, 74 mechanism, 418
Film, see Adsorbed film of bilayers, 409
First-hydration shell, 61 of biological membranes, 416-419
Flip-flop, 376, 377 of vesicles, 415
Flocculation, see Coagulation pathways, 418
Flock
particle density in, 120
Flory radius, 289 Gas
Fluctuation forces, 276, 288, 304, equations of state, 8, 23-24, 9 0 - 9 1 ,
405-408 112, 368
Fluidity, 387 PVT data, 8, 2 3 - 2 4
effect on forces, 404 Gas-liquid transition, 23-26, 29
of hydrocarbon chains, 404 Gauss' law, 35
of micelles, 383 Geometry of amphiphiles
of vesicles, 383 effect on micellar structure, 370, 381
Force, see also Interaction, Geometry of molecules
Intermolecular pair potential effect on interaction potentials,
definition, 5 - 6 117-119, 270-272
in relation to energy, 161-164 effect on melting and boiling points,
interdependence of different types, 115-116
155,412 Geometry of particles
range, 5 - 8 , 11-12, 152-154 effect on forces, 159
Force measuring techniques, 165-174 Gibbs-Helmholtz equation, 62
atomic force microscopy (AFM), Glass surface, see Silica surface
14-15, 173 Grahame equation, 234
compression (pressure) cell, 168 Grain boundaries, 93
direct methods, 14-15, 168-169 Gravitational force, 3 - 7 , 13-14, 21,
dynamic interactions, 172 145, 152, 192-194, 209
indirect methods, 165 G u o y - C h a p m a n equation, 239
mica" experiments, 169-173 G u o y - C h a p m a n theory, 239
osmotic pressure (OP), 168, 226
surface forces apparatus (SFA), 15,
169-172 Hamaker constant, 176-180, 189, 192,
total internal reflection microscopy 212, 267, 395
(TIRM), 172-173 based on addivity, 178, 188, 202-203
Forces, measurements of, 14-15, based on Lifshitz theory, 184-188,
165-174 192, 197
adhesion, 14-15, 166-168, 172, 397 effect of medium, 188-192, 396
capillary, 172 expressions for, 183-185, 188, 200,
colloidal, 167, 172-175 203-204, 396
D L V O , 172, 250-253, 397 for metals, 185, 204-206
double-layer, 250-253, 397, 401 for polymers, 196
entropic, 172, 407 measurement, 186-187, 190-191,
fluctuation, 407 197, 396
hydration, 172, 275-282, 401, 407 negative, 190-196
hydrophobic, 282-286, 409 nonretarded, 181-182, 186-187,
ion-correlation, 172, 397 190-191, 197
442 INDEX

Hamaker constant, continued origin, 5 9 - 6 0

retardation of, 196-198, 208 properties, 125-128
screening of, 199, 396 strength, 125, 128
values, 178, 186-191, 396 structure, 286
Hard core repulsion, 109-114 Hydrogen-bonding liquids, 59-60,
Head-groups, of amphiphiles, 342-343 125-127
area of, 367-369, 380, 412 Hydronium ion, 56
forces between, 311, 369, 382, Hydrophiolic, 54, 133
405-407, 420 group, 133-136
Helium films, 192-194 interaction, 133, 135
Hellman-Feynman theorem, 11 surface, 133-134,276
Helmholtz layer, 214, 222 Hydrophobicity, 2 2 - 2 3 , 122, 128-133,
Hertz theory, 328 283
History of intermolecular forces, 3 — 13 Hydrophobic
Hydrated ions, 55, 65, 121 bond, 132
Hydrated radius, 55, 121 effect, 96, 103, 128-131,283
Hydrated sizes of ions, 42, 55, 121 energy, 131, 354
Hydration, of ions, 42-44, 54-57, 61, group, 129, 133-136, 282-283
121, 281 interaction, 96, 103, 132-133, 136,
computer simulations, 121, 281 282-286, 367, 408-409
number, 55 solvation, 129
shell, 5 5 - 5 7 surface, 133-134, 282, 320, 409
Hydration force, 56, 57, 121, 226-227, Hydrophobic force, 131-133, 196,
230, 256, 261, 276-281, 403 282-286, 398
addivity of, 281 between bilayers, 408-409
attractive, 282 entropic contribution to, 133
between bilayers and membranes, examples of, 284
225-226, 276, 399-402 measurements, 282-286, 409
between colloidal particles, 275-282 origins, 284
in clays, 276, 279 Hygroscopic group, see hydrophilic
intrinsic, 401 group
limitation of, 402-405 Hysteresis
measurements, 276-279, 401 in adhesion, 322, 323, 329
origin of, 281-282, 285-286 in contact angle, 322
regulation of, 279-281, 400-401 in D L V O forces, 303
repulsive, 275-279 in polymer forces, 297
theoretical aspects, 281-282,
285-286, 402
Hydrocarbons
cohesive energy, 88-89 Ice
melting and boiling points, 115-116 dielectric constant, 82, 123
solubility, 2 2 - 2 3 , 129-133 hydrogen-bonds in, 124
Hydrocarbon-water interface, 22-23, lattice, 124
131-133, 316 properties, 82, 122-123
Hydrogen bond, 59-60, 116, 122-125, proton mobility in, 123
128, 132, 135, 142 Ideal gas, 8
directionality, 124-128 Ideal mixing, 2 0 - 2 2
examples, 124, 128 Image
in water, 59-60, 286 charge, 180-181
models of, 126 electrostatic, 180
 INDEX
field, 72, 180
force, 180-181, 256
Immiscibility, 22-23, 96, 102-103,
129 131, 196
of polymers, 142
Incommensurate surfaces, 205-206
Induced dipole, 67-70, 84
force, 75, 84
moment, 67-73
Induction force, 75-76, 94, 107
Instabilities, 14-15, 46, 175, 210
Interaction, see also Force,
Intermolecular pair potential
area of, 143
classification, 11-12, 27-29
definition, 12
effect of particle geometry, 155-163
of polar molecules, 57-58, 9 3 - 9 5
range of, 5 - 8 , 11-12
relative strengths of, 76, 9 4 - 9 5
Interdependence of forces, 155, 412
Interface, 92
liquid-liquid, 22-23, 313, 321, 324
liquid-vapour, 313
solid-liquid, 92, 313, 321, 324
solid-solid, 93
Interfacial energy (tension), 2 2 - 2 3 , 65,
131,144-145,267,313-315,350,367
effect of micelles, 365
values for, 315
Interfacial tension, 131, 314
Intermolecular pair potential, 5 - 1 1 ,
16-19, 28, 112-115, 121, 118-119,
139, 154, 566
angle-averaged, 60, 66, 74
exponential, 112
in liquid, 16-19, 118-119, 121, 154,
266, 276, 284, 405-407; see also
Solvation interaction
Lennard-Jones, 9, 14, 113-114
Mie, 8
power law, 112
summation of, 6, 203
Interparticle potentials, 154, 161-164,
177, 405
attractive hydrophobic, 284
cylinders, 163-165, 174, 177, 337
effect of particle geometry, 155, 161,
165, 177
fluctuation, 405-407
443
oscillatory, 266
repulsive hydration, 276
sphere-sphere, 157-159, 161-164,
177, 242-244, 257
sphere-surface, 157-158, 161-164,
177, 242-244, 257
Inverted micellar structures, 379,392,420
Ion
adsorption, 235, 400-401
binding, 33, 213-215, 243, 280,
400-401, 410
concentration at surface, 218-220,233
distribution, near a surface, 218-221,
231-233, 239-240
exchange, 214, 400-401
forces between, 33, 36, 121
hydration, 42-44, 56, 280, 400-401
in thin films, 220
size, 4 0 - 4 1 , 47, 110
solubility, 38-42, 47, 65
solvation, 37, 4 2 - 4 4
Ion hydration, 37, 42-44, 54-57, 61,
281,400-401
computer simulations, 220, 239, 281
number, 55
shell, 55
Ion-correlation force, 228, 397
lon-dipole interaction, 5 0 - 5 7
Ion-solvent interactions, 42-44, 54-57,
73-74
I o n - w a t e r interaction, 37, 4 2 - 4 4 ,
54-57, 73-74
Ionic bond, 33-36, 44, 46, 410
Ionic forces, 33-36, 410
Ionic crystal lattice, 35-36, 46, 142
Ionization potential, 84
Irreversibility, 324; see hysteresis
Isoelectric point, 237, 280
Johnson-Kendall-Roberts (JKR)
theory, 326
Keeson equation (in 2-D), 65
Keesom interaction, 62, 65, 75-76,
9 4 - 9 5 , 182, 256
Keesom orientation force, see Keesom
interaction
Kelvin equation, 331
444 INDEX

Kelvin radius, 331 structure at surfaces, 47, 272-275

Kinetic energy, 24-27 structure, 117-119, 272
Kinetic stability, 155 Liquid crystals, 121, 287
Liquid helium films, 192-194
Lock and key binding, 411-412
Langbein approximation, 159 London dispersion interaction, 90, 182
Langmuir equation, 229 London equation, 85, 88, 99, 101, 104,
Laplace pressure, equation, 195, 331 108, 113
Latent heat, 25-27, 86-87, 115 Long-range interaction (force), 5-8,
of alkanes, 89 11-12,30,37,62, 152-155,409
of van der Waals solids, 86-87 Long-range order, 30, 117-118
Lattice Lorenz-Lorentz equation, 79, 102
dipolar, 254-256 Lysolipids, 342
energy, 36 Lyotropic series, 280
ionic, 35-36
mismatch, 205-206
of charges, 35-36, 254-256 Madelung constant, 36
solid, 117 Magnetic force, 5
sum, 35-36, 254-256 Many-body effects, 16-19, 207
Lecithin, see Phosphatidylcholine Mass action, law of, 235
Lennard-Jones potential, 9, 14, 44, 46, McLachlan equation, 96
113, 175 Measurements
Lifshitz equation, 181, 197 of intersurface forces, 165-174
Lifshitz theory, 179-192; see also Medium effect, see Solvent effect
Hamaker constant Melting, 30, 115-116
limitations of, 209, 267 at a surface, 319
Ligand-receptor interaction, 411-412 of alkanes, 378
Lipid, 342-343, 387; see also of lipid chains, 378
Amphiphilic molecules Membrane, see Bilayer, Biological
biological, 387 membrane
compatibility of, 387 adhesion, 414
density, 413 fusion, 416-419
packing of, 387 pores in, 394
Lipid chains, 382 structure, 392
fluidity of, 383, 387 Meniscus forces, 331-333
Lipid packing Mesophase, 362
biological regulation of, 392 Metal oxide surface, 173
Lipid pores, 394 Metal surface, 204-206, 264
Lipid-protein interaction, 388-391 Metallic bonds, 31-32, 205
phase separation, 413 Micelle, 344, 346, 354, 371-372
Liposome, 363, 344 aggregation number, 372-373
Liquid cylindrical, 374
associated, 26, 59, 125-127, 268 dimensions, 372-373
boiling point, 115-116 disc-like, 349
computer simulations, 117 effect of temperature, 380
density, near surface, 261-264 end-effects, 374
freezing, 117 inverted, 379, 392, 420
melting, 115-18 ionic effects, 412
miscibility, 22-23 molecular packing in, 372
order in, 117-118, 121 polydispersity, 361, 373-374
 INDEX
pseudo-phase approximation, 365
rod-like, 349, 358-359, 374
size distribution, 358-362, 374
size regulation, 412
spherical, 349, 373
structure, 372
theoretical aspects, 371
Microemulsion, 380, 382, 412
Mie potential, 8, 266
Miscibility, 102-103, 142, 196
Molecular aggregates, 361; see also
Aggregates
Molecular packing, 93, 115
in thin films, 121
Molecular polarizability, 77
Molecular shape, 105, 115, 370, 381
Molecular size, 23, 110
Molecular theories, 4 3 - 4 6
Molecular dynamics simulation, 45, 92
Monolayer, 9 1 - 9 2 , 6 5 - 6 6
Monte Carlo simulation, 45, 220-221,
292
Multi-bilayers; see multilayer
Multilayer, 362-363
Negative adsorption, 147-148
Nernst equation, 21
Non-additive potentials, 84, 107
Non-aqueous colloids, 211
Non-aqueous liquids
forces in, 402
N o n - D L V O forces, 228, 253, 260
Non-equilibrium interactions, 297-299,
303-*304, 322-325, 329
Nonwetting, 149-151, 196-198
Olber's paradox, 14
Optimal headgroup area, 367-369
Order < lipid-protein, 413
in liquids, 17, 92, 117-119, 121
long range, 117-118, 121, 227
Ordering of molecules, 92
at surfaces, 17, 261-263, 272-275
in thin films, 261-263, 275, 287
Orientation-dependent interaction,
6 0 - 6 1 , 64, 105
dispersion force, 62, 105
polar molecules, 6 0 - 6 2
Orientation force, 76, 94, 107
445
Oscillatory force, 118-119, 121,
265-266, 272, 278-279, 284
effect of dipole moment, 273
effect of liquid, 261-263, 275, 287
effect of surfaces, 273, 287
potential of mean force, 118-119, 121
properties of, 269-275
Osmotic forces, 288, 304
Osmotic pressure of ions, 242
Osmotic pressure limit, 230, 244, 306
Outer Helmholz plane, 222, 253
Overlap force, 288, 294, 299, 405-407;
see also Steric interactions
Oxonium ion, 56
Packing
constraints, for amphiphiles, 370, 381
mismatch effects, 116
of molecules, 109-112, 115-116,
380-382
parameter, 381
Pair correlation function, 119
Pair potential, see Intermolecular pair
potential
Partial wetting, 149-151
Particle radius (size)
effect on adhesion, 143
Particle-surface interactions, 14, 147
Partitioning
of ions, 38, 103
of molecules, 103-104
Pauli exclusion principle, 29
Periodic structure, 362, 392
Peristaltic force, 307-309, 405-407
Phase diagrams
in relation to forces, 120
of hydrophobic substances, 136
Phase separation, 353
of polymers, 196
Phase transitions, 65-66, 93, 353
gas-liquid, 91-93, 6 5 - 6 6
in monolayers, 65-66
liquid-solid, 92
order-disorder, 91-92
Phosphatidylcholine, 342-343
Phospholipid, 342-343, 387; see also
Amphiphilic molecules
structure, 344
446 INDEX

Physical bond, 32, 46 in liquids, 16-19, 119

Point of zero charge, 237 law, Interaction potential
Poisson-Boltzmann equation, 215-216, Lennard-Jones, 9, 175
219, 222 power-law, 109
limitations of, 227-229 repulsive, 175
Poisson equation, 215 Potential of mean force, see
Polar molecule, 4 8 - 4 9 Intermolecular pair potential
interactions of, 50-64, 9 3 - 9 5 Potential of Stern- Helmholz layer, 223
polarizability of, 70 Pressure
self-energy, 50 between charged surfaces in solution,
solubility, 40, 65 221-223
Polarizability, atomic and molecular, between ions in solution, 221-223
6 7 - 7 1 , 7 9 - 8 1 , 96-98 disjoining, 192, 229
electronic, 6 7 - 6 9 Laplace, 195-331
excess, 76-78, 99 osmotic limit, 230, 244, 306
in medium, 76-78, 96, 99 Pressure distribution
molecular, 69-70, 76-81 in adhesive contact, 328
negative, 77-78 Primary minimum, 247-248
of bonds, 69 Protein, 172, 389
orientational, 70 aggregation, 388, 413
oscillator model, 97 in biological membranes, 389-392,413
values for, 69 interactions, 389, 413
Polarization force, 27, 75-76 structure, 391
Polydispersity Proton hopping in ice, water, etc. 123,286
effect on forces, 272 Protrusion of molecules
in micelle distribution, 358-362 decay length, 264, 305-307
Polymer, 290; see also Steric interactions energy, 263
abbreviations for, 290 force, 304-307, 405-407
adsorption, 291-293 'Pull-off' force, see adhesion force
bridging, 291
brush, 291-292
coverage, 292-293
grafted, 291-292 Quantum mechanical interaction, 11
immiscibility, 196 Quantum theory, 11
interactions, see Steric interactions Quartz surface, see Silica surface
loop, 291
melt, 290, 298
mushroom, 291-292 Radial distribution function, 19,117-119
random coil, 289-291 Radius
surface layer, 172 anion, 4 0 - 4 1 , 55, 110
tail, 291 atom, 109-112
train, 291 bare ion, 4 0 - 4 2 , 47, 55, 110
Polymer-covered surfaces, 292 calculations of, 23, 112
Potential distribution theorem, 60 cation, 4 0 - 4 1 , 55, 110
Potential function, 6-10, 16-19, 109, covalent bond, 110
113, 153; see also Intermolecular Flory, 289
pair potential hard sphere, 109-112
between ions, 121 hydrated, of ions, 42, 55, 109-112
exponential, 109 Kelvin, 331
hard sphere, 109 micelle, 379
 INDEX 447

molecule, 23, 109-112 Roughness, of surfaces, 260,263,273,288

of gyration, 289 dynamic, 273, 288
of ions, 4 0 - 4 1 , 55, 109-112 effect on adhesion, 329, 333
packing, 109-112 effect on interaction potential, 273
van der Waals, 109-112 static, 273, 288
vesicle, 379
Random close packing, 120
Random coil, 289-291
Range, offorces, 5 - 8 , 11-12, 36-37, 62, Sapphire, 172
152-155, 160, 174, 321 forces between, 252
Raoult's law, 103 Scaling
Rate of exchange, see exchange rate force with radius, 143
Rayleigh limit, 46 Schrodinger equation, 11
Reaction field, 72 Schultz-Hardy rule, 249-250
Reference state, 36, 54 Screened electric field, 37
Reflected field, 72, 180 Screening, of electrostatic forces, 37,199
Refractive index Secondary minimum, 247-248, 398
in relation to polarizability, 79-81 Self-assembly, 345-350; see also
Regulation Amphiphilic structures
of hydration forces, 279 theoretical aspects, 348
of surface charge, 230, 235-236 thermodynamics of 345, 365
Relative strength of different Self-association, see Self-assembly
interactions, 76 Self-energy, 18
Reptation, 92 and solubility, 103-104
Repeptization, 253 atom, 18, 103-105
Repulsive force, 145, 175, 192-194, 241, dipole, 50
256 ion, 37, 42, 63, 73
between polymers, 196 Shape, molecular, 115-116, 270-272
Born, 160 Short-range forces, 5-8, 11-12,
electrostatic, 256-257 152-155, 228
entropic, 407 between amphiphilic molecules, 361
hard core, 175 Short-range order, 117-118
head-group, 256, 311, 399, 405-408, Silica, colloidal properties of, 275
414-#16 Silica surface, 172, 320
hydration, 229, 256-257 forces between, 252, 279
solvation, 145 hydrophilicity of, 281, 320
steric, 160, 175 water films on, 320
van der Waals, 188-196, 256 wetting films on, 229, 281, 320
Repulsive potential, 112 Sizes of atoms and molecules, 22-23,
Reservoir ' 109-112
salt, electrolyte solution, 231 Size distribution
Residence time of aggregates, 354-362, 382
of amphiphiles, 375 of micelles, 360
of bound ions, 55-56 of vesicles, 384-385
of water, 5 5 - 5 6 Soap film, 276
Retarded van der Waals forces, forces within, 252
106-108, 194, 196 Solid-liquid transition, 92
Rotating dipolar molecules, 60-64, 81 Solubility, 22-23, 40, 64, 96, 102-105,
Rotational correlation time 136, 142
water, 56 in small volumes, 209
448 INDEX
Solubility, continued
in water, 2 2 - 2 3 , 38-42, 54-57,
129-131, 136, 353
of hydrocarbons, 22-23, 65, 129-132,
136
of ions, 38-42, 47, 54-57, 65
of water, 131, 136
parameter, 102-105
units of, 136
Solute-solvent miscibility, 102
Solvation force, 17, 56-57, 228, 261,
265-275; see also Hydration force
addivity of, 281
between ions, 121
computer simulation of, 121,265-266
effect of surface structure, 260-261,273
effect on surface energy, 267, 270
measurement, 269-275, 278-279
of mixtures, 271
origin, 17, 265
oscillatory, 121,261,265-266,278-279
properties of, 269-275
theories, 265-266
Solvation zone, 57
Solvent
effects on interactions, 16-19,142-146
effects on steric forces, 300
ideal, 291
ideal, for polymers, 289
theta, 291
Solvent effect, 16-17, 29, 144
Solvent structure, 17, 54, 57
Solvents
'good' and 'bad', 291
solubilities in, 2 2 - 2 3 , 40, 47, 136
Specific interaction, 128, 410
'lock and key', 411-412
biological, 411
bridging, 411
ionic, 410
ligand-receptor, 411-412
Spheres, interactions of, 157, 161, 177
Stability, of colloidal dispersion, 120,
247, 253, 257, 280, 287, 310, 333
Stern layer, 214, 222
effect on D L V O forces, 221-223,
252-253
potential, 222-223
Steric interactions (polymers), 29, 115,
276, 288, 293, 408; see also
Fluctuation force
attractive, 299
between bilayers, 311, 399, 402, 405
between brushes, 295-296, 302, 311
between chemisorbed layers, 297, 302
between grafted layers, 297, 299-302
between physisorbed layers, 297,
299-302
effect of coverage, 294, 299-302
effect of molecular weight, 296,
299-302
effect of solvent, 298-302
effect of temperature, 299-302
hysteresis effects in, 297, 299
in polymer melts, 298
in poor solvents, 299, 302
intersegment forces, 299
non-equilibrium aspects of, 303-304
range of, 298, 302
repulsive, 109
scaling, 299, 302
time effects in, 297, 303-304
Steric interactions (hard core), 160, 175
of atoms and molecules, 112-116,160
of head-groups, 311, 405-408
of surfaces, 175
Steric stabilization, 294, 310-311
Strength
of bonds, 32
of different forces, compared, 76,
127-128
Stress distribution
in adhesive contact, 328
Structural force, 17, 5 6 - 5 7 ; see
Solvation force
Structure
of liquids, 17, 117-119, 203, 270-272
of surfaces, 203, 323
Structured surfaces, 203, 287, 323
Surface
amphoteric, 236-238, 280
charge density, 217, 219, 239
charge regulation, 230, 235-236
charge, 213-215, 233-238, 255-258
charges, discrete, 254-256
dipoles, discrete, 254-256
hydrophilic, 133, 276
hydrophobic, 133, 282, 320
melting at, 319
potential, 233-236, 239-240
roughness, 260, 263, 288, 333
structured, 203, 255, 287, 323
 INDEX
Surface energy, 65, 144-145, 163, 179,
201-204, 258, 267, 312-317
in adhesion, 163, 178-179, 270, 313
of clusters, 317-318, 336
of curved surface, 270, 317, 333, 336
of metals, 204, 264, 313, 318.
of small droplets, 317-318, 336
of transfer, 317
theoretical aspects, 163, 179,
201-204, 258, 267, 313, 317-319
Surface forces apparatus (SFA), 169
Surface lattice, of charges, dipoles
forces between, 254-256
'. Surface roughness
dynamic, 273, 288
effect on forces, 273
static, 273, 288
{ Surface structure, 203
s effect on forces, 205, 273
Surface tension, 8, 131, 201-204, 258,
312-313; see also Surface energy
values for, 315
Surfaces used in force measurements,
14, 173
Surfactant, see Amphophilic molecules
Susceptibility, 74
Swelling, 253
bilayer, 226-227
clay, 226-227
Temperature.
chain meltirig, 378
effect on forces, 61-64, 285, 404
theta, 291
Thermal energy, 2 4 - 2 7
Thermal fluctuation forces; see
Fluctuation forces
Thermodynamic equilibrium, 16, 150,
163, 212, 231,244
Theta solvent, 291
Theta temperature, 291
Three-body forces, 107
Tip-surface interaction, 14
Transition temperature of chains, 378
Trivalent ions
adsorption of, 237
Trouton's rule, 26, 30, 115
Twist angle
between two surfaces, 205
449
Two dimensions, interactions in, 65-66
equations of state, 29, 91
phase transitions, 29, 66
Undulation force, 307-309, 403-407
Unification of forces, 75-76
van der Waals
bond energy, 88, 104
dispersion force, 8 3 - 8 9
equation of state, 8, 23-24, 66,
9 0 - 9 1 , 112
gas, 8, 23
liquid, 8 5 - 8 6
radius, 109-112
self-energy, 50, 103-105
solid, 8 5 - 8 6
van der Waals force, 8, 29, 76, 94, 225,
228, 246
across thin films, 192-194, 202
additivity of, 89, 106, 177-179, 202
at small separations, 267-268
between atoms, and molecules,
93-96, 128, 196
between bilayers and membranes,
199, 212, 225, 395-396
between hydrocarbons, 88-89,
201-204, 395-396
between macroscopic bodies, 169, 177
between metals, 185, 201-204
calculation, 86-87, 95, 180-182
contribution to surface energy,
178-179, 201-204
dispersion contribution, 83-89,
93-96, 128
effect of adsorbed films, 206
effect of medium, 99-102, 180-182,
188-192
in adhesion, 178-179, 201-204
in relation to other interactions, 128
in salt solutions, 199, 395-396
Lifshitz theory of, 179-192
measurement, 169, 186-191,
197-199, 207-209, 396
of alkanes, 8 8 - 8 9
of chain molecules, 8 8 - 8 9
origin, 84
potential, 62
repulsive, 192-198
450
van der Waals force, continued
retardation of, 106, 108, 194,
196-198,208, 396
screening of, 199, 396
simple expression for, 85, 94, 101,
177, 395-396
strength of, 85-87, 94, 128, 178-179
theories of, 85, 96, 179
Vapour pressure, 26-27, 194-195, 229,
331
Vesicle, 344, 361, 378-379, 382-385
adhesion of, 172, 414-416
critical aggregation concentration, 364
deformation, 416
dimensions, 379, 344
forces between, 172, 417
fusion, 415-417
interactions, 414-416
size distribution, 384-385
size, 379-385
theoretical aspects, 378-379, 382-385
Viscosity, effect on forces, 47
Water, see also Hydration forces
adsorbed films, 256-257
as solvent, 52-53, 65
at surfaces, 217-218
bound lifetime, 55-56
dielectric constant, 82, 123
effect on adhesion, 271
INDEX
hydrogen bonds in, 59-60, 286
Lennard-Jones potential for, 126
models for, 125-126
orientation effects, 64
proton mobility in, 123, 286
rotational correlation time, 56
small clusters of, 319
solubility, 22-23, 65, 103
special interactions of, 59-60, 64,
122-125, 281-286
special properties of, 59, 79, 82, 94,
96,103,116,122-125,135-136,275
'ST2' model, 126
structure, 129-131, 135, 217
Weak overlap approximation, 242
Wetting, see also Adsorbed liquid film
critical point, 151
films, 149-151, 192-194, 198, 210,
229, 257, 281, 319, 322
Work
of adhesion, 313
of cohesion, 313
Young equation, 150, 321
Young-Dupre equation, 150, 321
Zwitterion, 48, 52, 342-344
interactions of, 256, 277, 402, 404