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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
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
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
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
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
436
INDEX 437
Surface energy, 65, 144-145, 163, 179, Two dimensions, interactions in, 65-66
201-204, 258, 267, 312-317 equations of state, 29, 91
in adhesion, 163, 178-179, 270, 313 phase transitions, 29, 66
of clusters, 317-318, 336
of curved surface, 270, 317, 333, 336
of metals, 204, 264, 313, 318. Undulation force, 307-309, 403-407
of small droplets, 317-318, 336 Unification of forces, 75-76
of transfer, 317
theoretical aspects, 163, 179,
201-204, 258, 267, 313, 317-319 van der Waals
Surface forces apparatus (SFA), 169 bond energy, 88, 104
Surface lattice, of charges, dipoles dispersion force, 8 3 - 8 9
forces between, 254-256 equation of state, 8, 23-24, 66,
'. Surface roughness 9 0 - 9 1 , 112
dynamic, 273, 288 gas, 8, 23
effect on forces, 273 liquid, 8 5 - 8 6
static, 273, 288 radius, 109-112
{ Surface structure, 203 self-energy, 50, 103-105
s effect on forces, 205, 273 solid, 8 5 - 8 6
Surface tension, 8, 131, 201-204, 258, van der Waals force, 8, 29, 76, 94, 225,
312-313; see also Surface energy 228, 246
values for, 315 across thin films, 192-194, 202
Surfaces used in force measurements, additivity of, 89, 106, 177-179, 202
14, 173 at small separations, 267-268
Surfactant, see Amphophilic molecules between atoms, and molecules,
Susceptibility, 74 93-96, 128, 196
Swelling, 253 between bilayers and membranes,
bilayer, 226-227 199, 212, 225, 395-396
clay, 226-227 between hydrocarbons, 88-89,
201-204, 395-396
between macroscopic bodies, 169, 177
between metals, 185, 201-204
Temperature. calculation, 86-87, 95, 180-182
chain meltirig, 378 contribution to surface energy,
effect on forces, 61-64, 285, 404 178-179, 201-204
theta, 291 dispersion contribution, 83-89,
Thermal energy, 2 4 - 2 7 93-96, 128
Thermal fluctuation forces; see effect of adsorbed films, 206
Fluctuation forces effect of medium, 99-102, 180-182,
Thermodynamic equilibrium, 16, 150, 188-192
163, 212, 231,244 in adhesion, 178-179, 201-204
Theta solvent, 291 in relation to other interactions, 128
Theta temperature, 291 in salt solutions, 199, 395-396
Three-body forces, 107 Lifshitz theory of, 179-192
Tip-surface interaction, 14 measurement, 169, 186-191,
Transition temperature of chains, 378 197-199, 207-209, 396
Trivalent ions of alkanes, 8 8 - 8 9
adsorption of, 237 of chain molecules, 8 8 - 8 9
Trouton's rule, 26, 30, 115 origin, 84
Twist angle potential, 62
between two surfaces, 205 repulsive, 192-198
450 INDEX
van der Waals force, continued hydrogen bonds in, 59-60, 286
retardation of, 106, 108, 194, Lennard-Jones potential for, 126
196-198,208, 396 models for, 125-126
screening of, 199, 396 orientation effects, 64
simple expression for, 85, 94, 101, proton mobility in, 123, 286
177, 395-396 rotational correlation time, 56
strength of, 85-87, 94, 128, 178-179 small clusters of, 319
theories of, 85, 96, 179 solubility, 22-23, 65, 103
Vapour pressure, 26-27, 194-195, 229, special interactions of, 59-60, 64,
331 122-125, 281-286
Vesicle, 344, 361, 378-379, 382-385 special properties of, 59, 79, 82, 94,
adhesion of, 172, 414-416 96,103,116,122-125,135-136,275
critical aggregation concentration, 364 'ST2' model, 126
deformation, 416 structure, 129-131, 135, 217
dimensions, 379, 344 Weak overlap approximation, 242
forces between, 172, 417 Wetting, see also Adsorbed liquid film
fusion, 415-417 critical point, 151
interactions, 414-416 films, 149-151, 192-194, 198, 210,
size distribution, 384-385 229, 257, 281, 319, 322
size, 379-385 Work
theoretical aspects, 378-379, 382-385 of adhesion, 313
Viscosity, effect on forces, 47 of cohesion, 313