分子间力和表面力 原书第3版 文版PDF|Epub|txt|kindle电子书版本下载

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PART ONE THE FORCES BETWEEN ATOMS AND MOLECULES1

1．Historica l Perspective3

1.1．The Four Forces of Nature3

1.2．Greek and Medieval Notions of Intermolecular Forces3

1.3．The Seventeenth Century:First Scientific Period5

1.4．The Eighteenth Century:Confusion,Contradictions,and Controversy7

1.5．The Nineteenth Century:Continuum versus Molecular Theories8

1.6．Intermolecular Force-Laws and Interaction Potentials:Long-and Short-Range Forces9

1.7．First Successful Phenomenological Theories12

1.8．First Estimates of Molecular Sizes15

1.9．The Twentieth Century:Understanding Simple Systems16

1.10．Recent Trends17

Problems and Discussion Topics18

2．Thermodynamic and Statistical Aspects of Intermolecular Forces23

2.1．The Interaction of Molecules in Free Space and in a Medium23

2.2．Self-Energy and Pair Potential25

2.3．The Boltzmann Distribution and the Chemical Potential26

2.4．The Distribution of Molecules and Particles in Systems at Equilibrium27

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 Interaction31

2.7．Classification of Forces and Pair Potentials34

2.8．Theoretical Analyses of Multimolecular Systems:Continuum and Molecular Approaches35

2.9．Molecular Approaches via Computer Simulations:Monte Carlo(MC)and Molecular Dynamics(MD)37

2.10．Newton's Laws Applied to Two-Body Collisions39

2.11．Kinetic and Statistical Aspects of Multiple Collisions:the Boltzmann Distribution43

Problems and Discussion Topics49

3．Strong Intermolecular Forces:Covalent and Coulomb Interactions53

3.1．Covalent or Chemical Bonding Forces53

3.2．Physical and Chemical Bonds54

3.3．Coulomb Forces or Charge-Charge Interactions,Gauss's Law55

3.4．Ionic Crystals58

3.5．Reference States59

3.6．Range of Electrostatic Forces60

3.7．The Born Energy of an Ion61

3.8．Solubility of Ions in Difierent Solvents62

3.9．Specific Ion-Solvent Effects:Continuum Approach66

3.10．Molecular Approach:Computer Simulations and Integral Equations of Many-Body Systems67

ProblemsandDiscussion Topics68

4．Interactions Involving Polar Molecules71

4.1．What Are Polar Molecules?71

4.2．Dipole Self-Energy73

4.3．Ion-Dipole Interactions73

4.4．Ions in Polar Solvents78

4.5．Strong Ion-Dipole Interactions in Water:Hydrated Ions78

4.6．Solvation Forces,Structural Forces,and Hydration Forces80

4.7．Dipole-Dipole Interactions81

4.8．Magnetic Dipoles83

4.9．Hydrogen Bonds83

4.10．Rotating Dipoles and Angle-Averaged Potentials84

4.11．Entropic Effects86

Problems and Discussion Topics88

5．Interactions Involving the Polarization of Molecules91

5.1．The Polarizability ofAtoms and Molecules91

5.2．The Polarizability of Polar Molecules93

5.3．Other Polarization Mechanisms and the Effects of Polarization on Electrostatic Interactions94

5.4．Interactions between Ions and Uncharged Molecules96

5.5．Ion-Solvent Molecule Interactions and the Born Energy98

5.6．Dipole-Induced Dipole Interactions99

5.7．Unification of Polarization Interactions99

5.8．Solvent Efiects and"Excess Polarizabilities"100

Problems and Discussion Topics105

6．Van der Waals Forces107

6.1．Origin of the Van der Waals-dispersion Force between Neutral Molecules:the London Equation107

6.2．Strength of Dispersion Forces:Van der Waals Solids and Liquids109

6.3．Van der Waals Equation of State113

6.4．Gas-Liquid and Liquid-Solid Phase Transitions in 3D and 2D115

6.5．Van der Waals Forces between Polar Molecules117

6.6．General Theory of Van der Waals Forces between Molecules119

6.7．Van der Waals Forces in a Medium122

6.8．Dispersion Self-Energy of a Molecule in a Medium126

6.9．Further Aspects of Van der Waals Forces:Anisotropy(Orientation),Nonadditivity(Many-Body),and Retardation Efiects127

Problems and Discussion Topics130

7．Repulsive Steric Forces,Total Intermolecular Pair Potentials,and Liquid Structure133

7.1．Sizes of Atoms,Molecules,and Ions133

7.2．Repulsive Potentials136

7.3．Total Intermolecular Pair Potentials:Their Form,Magnitude,and Range136

7.4．Role of Repulsive Forces in Noncovalently Bonded Solids140

7.5．Packing of Molecules and Particles in Solids142

7.6．Role of Repulsive Forces in Liquids:Liquid Structure145

7.7．The Effect of Liquid Structure on Molecular Forces147

Problems and Discussion Topics148

8．Special Interactions:Hydrogen-Bonding and Hydrophobic and Hydrophilic Interactions151

8.1．The Unique Properties of Water151

8.2．The Hydrogen Bond152

8.3．Models of Water and Associated Liquids156

8.4．Relative Strengths of Different Types of Interactions157

8.5．The Hydrophobic Effect158

8.6．The Hydrophobic Interaction161

8.7．Hydrophilic Interactions163

Problems and Discussion Topics166

9．Nonequilibrium and Time-Dependent Interactions169

9.1．Time-and Rate-Dependent Interactions and Processes169

9.2．Rate-and Time-Depended Detachment(Debonding)Forces171

9.3．Energy Transfer(Dissipation)during Molecular Collisions:the Deborah Number175

9.4．Energy Transfer during Cyclic Bonding-Unbonding Processes178

9.5．Relationships between Time,Temperature,and Velocity(Rate)in Complex Processes182

Problems and Discussion Topics185

PART TWO THE FORCES BETWEEN PARTICLES AND SURFACES189

10．Unifying Concepts in Intermolecular and Interparticle Forces191

10.1．The Association of Like Molecules or Particles in a Medium191

10.2．Two Like Surfaces Coming Together in a Medium:Surface and Interfacial Energy196

10.3．The Association of Unlike Molecules,Particles,or Surfaces in a Third Medium197

10.4．Particle-Surface and Particle-Interface Interactions198

10.5．Engulfing and Ejection200

10.6．Adsorbed Surface Films:Wetting and Nonwetting201

Problems and Discussion Topics203

11．Contrasts between Intermolecular,Interparticle,and Intersurface Forces205

11.1．Short-Range and Long-Range Effects of a Force:Qualitative Difierences in the Interactions of Particles and Small Molecules205

11.2．Interaction Potentials between Macroscopic Bodies208

11.3．Effective Interaction Area of Two Spheres:the Langbein Approximation211

11.4．Interactions of Particles Compared to Those between Atorms or Small Molecules212

11.5．Interaction Energies and Interaction Forces:the Derjaguin Approximation215

11.6．"Body Forces"and"Surface Forces"220

Problems and Discussion Topics220

12．Force-Measuring Techniques223

12.1．Direct and Indirect Measurements of Intermolecular,Interparticle,and Surfaca Forces223

12.2．Difierent Direct Force-Measuring Techniques227

12.3．Mechanics of Direct Force Measurements and Problems of Interpretation231

12.4．Measuring Force-Distance Functions,F(D)234

12.5．Instabilities235

12.6．Measuring Adhesion Forces and Energies237

12.7．Measuring Forces between Macroscopic Surfaces:the SFA,OP/OS and Related Techniques239

12.8．Measuring Forces between Microscopic(Colloidal)and Nanoscopic Particles:AFM and TIRM Techniques245

12.9．Measuring Single-Molecule and Single-Bond Interactions:OT and MC Techniques248

Problems and Discussion Topics250

13．Van der Waals Forces between Particles and Surfaces253

13.1．Van der Waals Force-Laws for Bodies of Different Geometries:the Hamaker Constant253

13.2．Strength of Van der Waals Forces between Bodies in a Vacuum or Air255

13.3．The Lifshitz Theory of Van der Waals Forces256

13.4．Particle-Surface Interactions259

13.5．Nonretarded Hamaker Constants Calculated on the Basis of the Lifshitz Theory260

13.6．Van der Waals Forces between Conducting Media261

13.7．Theoretical and Experimental Hamaker Constants for Interactions in a Vacuum or Air263

13.8．Applications of the Lifshitz Theory to Interactions in a Medium264

13.9．Repulsive Van der Waals Forces:Disjoining Pressure and Wetting Films267

13.10．Van der Waals Forces at Large Separations:Retardation Effects270

13.11．Electrostatic Screening Effects in Electrolyte Solutions274

13.12．Combining Relations274

13.13．Surface and Adhesion Energies275

13.14．Surface Energies of Metals280

13.15．Forces between Surfaces with Adsorbed Layers281

13.16．Experiments on Van der Waals Forces282

Problems and Discussion Topics284

14．Electrostatic Forces between Surfaces in Liquids291

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)Equation293

14.4．Surface Charge,Electric Field,and Counterion Concentration at a Surface:"Contact"Values294

14.5．Counterion Concentration Profile Away from a Surface296

14.6．Origin of the Ionic Distribution,Electric Field,Surface Potential,and Pressure298

14.7．The Pressure between Two Charged Surfaces in Water:the Contact Value Theorem300

14.8．Limit of Large Separations:Thick Wetting Films303

14.9．Limit of Small Separations:Osmotic Limit and Charge Regulation305

14.10．Charged Surfaces in Electrolyte Solutions306

14.11．The Grahame Equation308

14.12．Surface Charge and Potential of Isolated Surfaces309

14.13．Effect of Divalent Ions311

14.14．The Debye Length312

14.15．Variation of Potential ψx and Ionic Concentrations px Away from a Surface313

14.16．Electrostatic Double-Layer Interaction Forces and Energies between Various Particle Surfaces314

14.17．Exact Solutions for Constant Charge and Constant Potential Interactions:Charge Regulation318

14.18．Asymmetric Surfaces321

14.19．Ion-Condensation and Ion-Correlation Forces322

14.20．More Complex Systems:Finite Reservoir Systems and Finite Ion-Size Efiects325

14.21．Van der Waals and Double-Layer Forces Acting Together:the DLVO Theory326

14.22．Experimental Measurements of Double-Layer and DLVO Forces331

14.23．Electrokinetic Forces334

14.24．Discrete Surface Charges and Dipoles335

Problems and Discussion Topics338

15．Solvation,Structural,and Hydration Forces341

15.1．Non-DLVO Forces341

15.2．Molecular Ordering at Surfaces,Interfaces,and in Thin Films342

15.3．Ordering of Spherical Molecules between Two Smooth(Unstructured)Surfaces345

15.4．Ordering of Nonspherical Molecules between Structured Surfaces347

15.5．Origin of Main Type of Solvation Force:the Oscilatory Force349

15.6．Jamming354

15.7．Experimental Measurements and Properties of Oscillatory Forces355

15.8．Solvation Forces in Aqueous Systems:Monotonically Repulsive"Hydration"Forces361

15.9．Solvation Forces in Aqueous Systems:Attractive"Hydrophobic"Forces370

Problems andDiscussion Topics378

16．Steric(Polymer-Mediated)and Thermal Fluctuation Forces381

16.1．Diffuse Interfaces in Liquids381

16.2．The States of Polymers in Solution and at Surfaces381

16.3．Repulsive"Steric"or"Overlap"Forces between Polymer-Covered Surfaces387

16.4．Interparticle Forces in Pure Polymer Liquids(Polymer Melts)393

16.5．Attractive"Intersegment"and"Bridging"Forces394

16.6．Attractive"Depletion"Forces398

16.7．Polyelectrolytes402

16.8．Nonequilibrium Aspects of Polymer Interactions404

16.9．Thermal Fluctuations of and Forces between Fluid-Like Interfaces405

16.10．Short-Range Protrusion Forces406

16.11．Long-Range Undulation Forces408

Problems and Discussion Topics411

17．Adhesion and Wetting Phenomena415

17.1．Surface and Interfacial Energies415

17.2．Adhesion Energies versus Adhesion Forces419

17.3．Highly Curved Surfaces and Interfaces:Clusters,Cavities,and Nanoparticles422

17.4．Contact Angles and Wetting Films429

17.5．Wetting of Rough,Textured,and Chemically Heterogeneous Surfaces434

17.6．Contact Angle Hysteresis439

17.7．Adhesion of Solid Particles:the JKR and Hertz Theories442

17.8．Adhesion Hysteresis448

17.9．Adhesion of Rough and Textured Surfaces452

17.10．Plastic Deformations453

17.11．Capillary Forces456

Problems and Discussion Topics461

18．Friction and Lubrication Forces469

18.1．Origin of Friction and Lubrication Forces469

18.2．Relationship between Adhesion and Friction Forces476

18.3．Amontons'Laws of(Dry)Friction481

18.4．Smooth and Stick-Slip Sliding482

18.5．Lubricated Sliding485

18.6．Transitions between Liquid-and Solid-Like Films490

18.7．The"Real"Area of Contact of Rough Surfaces493

18.8．Rolling Friction494

18.9．Theoretical Modeling of Friction Mechanisms495

Problems and Discussion Topics497

PART THREE SELF-ASSEMBLING STRUCTURES AND BIOLOGICAL SYSTEMS501

19．Thermodynamic Principles of Self-Assembly503

19.1．Introduction:Soft Structures503

19.2．Fundamental Thermodynamic Equations of Self-Assembly504

19.3．Conditions Necessary for the Formation of Aggregates509

19.4．Effect of Dimensionality and Geometry:Rods,Discs,and Spheres510

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 Transfer514

19.8．Nucleation and Growth ofAggregates515

19.9．2D Structures on Surfaces:Soluble and Insoluble Monolayers520

19.10．Line Tension and 2D Micelles(Domains)521

19.11．Soluble Monolayers and the Gibbs Adsorption Isotherm524

19.12．Size Distributions of Self-Assembled Structures524

19.13．Large and More Complex Amphiphilic Structures527

19.14．Effects of Interactions between Aggregates:Mesophases and Multilayers528

Problems and Discussion Topics530

20．Soft and Biological Structures535

20.1．Introduction:Equilibrium Considerations of Fluid Amphiphilic Structures535

20.2．Optimal Headgroup Area536

20.3．Geometric Packing Considerations538

20.4．Spherical Micelles540

20.5．Nonspherical and Cylindrical Micelles543

20.6．Bilayers544

20.7．Vesicles548

20.8．Curvature/Bending Energies and Elasticities of Monolayers and Bilayers550

20.9．Other Amphiphilic Structures and the Transitions between Them558

20.10．Self-Assembly on Surfaces and Interfaces:2D Micelles,Domains,and Rafts562

20.11．Biological Membranes564

20.12．Membrane Lipids564

20.13．Membrane Proteins and Membrane Structure567

Problems and Discussion Topics569

21．Interactions of Biological Membranes and Structures577

21.1．Van der Waals Forces577

21.2．Electrostatic(Double-Layer)and DLVO Forces579

21.3．Repulsive Entropic(Thermal Fluctuation,Steric-Hydration)Forces:Protrusion,Headgroup Overlap,and Undulation Forces585

21.4．Attractive Depletion Forces593

21.5．Attractive Hydrophobic Forces595

21.6．Biospecificity:Complementary,Site-Specifc and Ligand-Receptor(LR)Interactions599

21.7．Bridging(Tethering)Forces603

21.8．Interdependence of Intermembrane and Intramembrane Forces605

21.9．Biomembrane Adhesion,Bioadhesion607

21.10．Membrane Fusion611

Problems and Discussion Topics613

22．Dynamic Biointeractions617

22.1．Subtleties of Biological Forces and Interactions617

22.2．Interactions that Evolve in Space and Time:Some General Considerations617

22.3．Biological Rupture and Capture:The Bell and Jarzynski Equations619

22.4．Multiple Bonds in Series and in Parallel622

22.5．Detachment versus Capture Processes:Biological Importance of"Rare Events"626

22.6．Dynamic Interactions between Biological Membranes and Biosurfaces626

22.7．Self-Assembly versus Directed Assembly:Dynamic Phases and Tunable Materials628

22.8．Motor Proteins,Transport Proteins,and Protein Engines630

Problems and Discussion Topics631

References635

Index661