Fundamentals and Practice in Statistical Thermodynamics

Jianzhong Wu, PhD, is a professor in the Department of Chemical and Environmental Engineering at the University of California, Riverside. He also serves as collaborating faculty in the Departments of Bioengineering, Materials Science and Engineering, and Mathematics. Dr. Wu is an elected fellow of the American Physical Society and the American Institute for Medical and Biological Engineering. John M. Prausnitz, PhD, is a professor of chemical engineering at the University of California, Berkeley. He is a member of the National Academy of Sciences, National Academy of Engineering, and American Academy of Arts and Sciences. He is also a recipient of the National Medal of Science in recognition of his pioneering work on engineering-oriented molecular thermodynamics.

• Preface xixAbout the Companion Website xxi1 Microscopic Origin of Thermodynamics 11.1 Microscopic Constituents of Thermodynamic Systems 11.2 Thermodynamic Relations 51.3 Microscopic Uncertainty, Ensemble Average, and Ergodicity 101.4 Entropy and Information 151.5 Ab initio Thermodynamics 211.6 Statistical-Thermodynamic Models 241.7 Additivity and Relativity in Thermodynamics 29Chapter Summary 32Further Readings 33Problems 332 Statistical Ensembles and MD Simulation 392.1 Microcanonical Ensemble 392.2 Basics of MD Simulation 452.3 Canonical Ensemble 502.4 Thermostat Methods 542.5 The Langevin Dynamics 592.6 Fluctuation–Dissipation Theorem 642.7 Isobaric–Isothermal Ensemble 682.8 Isobaric Molecular Dynamics 732.9 Grand Canonical Ensemble 762.10 Transformation Between Ensembles 802.11 Generalized Ensembles 85Chapter Summary 89Further Readings 93Problems 943 Ideal Gases and Single-Molecule Thermodynamics 1053.1 Noninteracting Molecular Systems 1053.2 Monatomic Ideal Gases 1083.3 Diatomic Molecules 1163.4 Polyatomic Molecules 1233.5 Chemical Equilibrium in Ideal-Gas Mixtures 1283.6 Thermodynamics of Gas Adsorption 1323.7 Thermodynamics of Gas Hydrates 1393.8 Ideal Polymer Chains 1453.9 Gaussian Chains 1523.10 Statistics of Copolymer Chains 1573.11 Semi-Flexible Chains 1593.12 Random-Walk Models 164Chapter Summary 171Further Readings 172Problems 1734 Thermodynamics of Photons, Electrons, and Phonons 1874.1 Quantum Particles 1874.2 Quantum Statistics 1924.3 Thermodynamics of Light 1974.4 Radiation and Solar Energy Conversion 2034.5 The Free-Electron Model of Metals 210Chapter Summary 228Further Readings 229Problems 2295 Cooperative Phenomena and Phase Transitions 2415.1 Spins and Ferromagnetism 2425.2 The Ising Chain Model 2435.3 Ionization of Weak Polyelectrolytes 2515.4 The Zimm–Bragg Model of Helix-Coil Transition 2575.5 Two-Dimensional Ising Model 2625.6 Mean-Field Methods 2685.7 Lattice Models 2745.8 Order Parameters and Phase Transitions 2835.9 The Landau Theory of Phase Transitions 2885.10 Microemulsion and Liquid Crystals 2975.11 Critical Phenomena and Universality 3015.12 Renormalization Group (RG) Theory 3065.13 Generalized Ising Models 316Chapter Summary 320Further Readings 325Problems 3256 Monte Carlo Simulation 3376.1 Importance Sampling 3386.2 Monte Carlo Sampling 3436.3 The Metropolis–Hastings Algorithm 3486.4 Monte Carlo Simulation for an Ising Chain 3516.5 Simulation Size 3546.6 mc Simulation for Simple Fluids 3606.7 Biased MC Sampling Methods 3656.8 Free-Energy Calculation Methods 3726.9 Simulation of Crystalline Solids 3776.10 Monte Carlo Simulation of Fluid Phase Equilibria 3856.11 Histogram Reweighting Analysis 3936.12 Enhanced Sampling Methods 404Chapter Summary 417Further Readings 421Problems 4217 Simple Fluids and Colloidal Dispersions 4297.1 Microstates in the Phase Space 4297.2 Radial Distribution Function and Structure Factor 4347.3 Structure–Property Relations 4417.4 Integral Equation Theories 4487.5 Hard-Sphere Model 4557.6 The Sticky Hard-Sphere Model of Colloids and Globular Proteins 4637.7 The van der Waals Theory 4677.8 The Cell Model for Colloidal Crystals 4747.9 Order Through Entropy 4787.10 Colloidal Phase Diagrams and Protein Crystallization 4817.11 Perturbation Theories 4857.12 Critical Behavior of Fluid–Fluid Transition 4977.13 Molecular Theory of Critical Phenomena 503Chapter Summary 511Further Readings 521Problems 5218 Polymer Solutions, Blends, and Complex Fluids 5378.1 The Flory–Huggins Theory 5378.2 Phase Behavior of Polymer Solutions and Blends 5458.3 Statistical Mechanics of Polymeric Fluids 5538.4 Equations of State for Hard-Sphere Chains 5638.5 Statistical Associating Fluid Theory (SAFT) 5788.6 Random-Phase Approximation 5868.7 Continuous Gaussian Chains Model and the Polymer Field Theory 591Chapter Summary 598Further Readings 618Problems 6189 Solvation, Electrolytes, and Electric Double Layer 6359.1 The McMillan–Mayer Theory 6359.2 Phenomenological Solvation Models 6459.3 Solvent-Mediated Potentials and Colloidal Forces 6549.4 Electrostatics in Dilute Electrolytes 6649.5 Extended Debye–Hückel Models 6719.6 Integral-Equation Theories for Ionic Systems 6799.7 Statistical Behavior of Polyelectrolyte Chains 6919.8 The Cell Model and Counterion-Condensation Theory 6979.9 Liquid-State Theories of Polyelectrolyte Solutions 7049.10 Electric Double Layer (EDL) 710Chapter Summary 718Further Readings 720Problems 720Index 735