Molecular Theory of Capillarity

Principal symbols ix Mechanical Molecular Models Introduction 1(1) Molecular mechanics 2(5) Capillary phenomena 7(6) The internal energy of a liquid 13(3) The continuous surface profile 16(1) The mean molecular field 17(8) Thermodynamics Thermodynamics and kinetic theory 25(1) The thermodynamics of the surface 26(5) Surface functions 31(7) The spherical surface 38(5) Quasi-thermodynamics---a first look 43(7) The Theory of Van Der Waals Introduction 50(6) The surface tension 56(1) Independently variable densities 57(5) Gibbs adsorption equation in the van der Waals theory 62(2) Constraints on the range of fluctuations 64(5) Statistical Mechanics of the Liquid-Gas Surface Introduction 69(1) Distribution and correlation functions 69(16) The pressure tensor 85(4) The virial route to the surface tension 89(4) Functionals of the distribution functions 93(5) The surface tension from the direct correlation function 98(6) Equivalence of the two expressions for the surface tension 104(5) The spherical surface 109(6) Density fluctuations and their correlation 115(7) Local thermodynamic functions 122(7) Model Fluids in the Mean-Field Approximation Introduction: mean-field theory of a homogeneous fluid of attracting hard spheres 129(4) Liquid--gas interface in the model of attracting hard spheres 133(2) Lattice--gas model: one component 135(5) Lattice--gas model: two components 140(11) Penetrable-sphere model: theory 151(8) Penetrable-sphere model: applications 159(8) Penetrable-sphere model: spherical surfaces 167(6) Computer Simulation of the Liquid--Gas Surface The experimental background 173(2) The methods of computer simulation 175(3) The density profile 178(3) The surface tension 181(4) Further work 185(5) Calculation of the Density Profile Introduction 190(1) Solution of the YBG equation 190(5) Approximations for the direct correlation function 195(3) Modified van der Waals theories 198(2) Perturbation theories 200(2) Surface tension 202(5) Three-Phase Equilibrium Introduction 207(2) Contact angles and Neumann's triangle 209(3) Spreading and Antonow's rule 212(9) The αγ interface 221(4) Phase transitions in interfaces. The Cahn transition 225(7) Three-phase line and line tension 232(17) Interfaces Near Critical Points Introduction: mean-field approximation 249(6) Digression on the Ornstein-Zernike theory of the pair-correlation function 255(6) Digression on critical-point exponents 261(9) Van der Waals theory with non-classical exponents 270(6) Tricritical points 276(9) Non-critical interface near a critical endpoint 285(11) Renormalization-group theory; field-theoretical models 296(11) Appendix 1 Thermodynamics 307(7) Appendix 2 Dirac's delta-function 314(2) Name Index 316(5) Subject Index 321