This is an account mostly of what I have seen and worked on in physical chemistry, from my time in graduate school six decades ago to the present. It is a personal story about kinetics, thermodynamics, and statistical mechanics—in which subjects I continue to be educated, thanks to patient instruction by my students and associates.

When I had the invitation from Steve Leone to write this article I said “yes” because (a) “yes” is my default setting; (b) it was a great honor to have been invited to do it; and (c) I was too busy at the time to think about what the consequences of saying “yes” would be. I must now do my best to fulfill my promise.


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Literature Cited

  1. Yang CN, Lee TD. 1.  1952. Statistical theory of equations of state and phase transitions. I. Theory of condensation. Phys. Rev. 87:404–9 [Google Scholar]
  2. Lee TD, Yang CN. 2.  1952. Statistical theory of equations of state and phase transitions. II. Lattice gas and Ising model. Phys. Rev. 87:410–19 [Google Scholar]
  3. Onsager L. 3.  1944. Crystal statistics. I. A two-dimensional model with an order-disorder transition. Phys. Rev. 65:117–49 [Google Scholar]
  4. Guggenheim EA. 4.  1945. The principle of corresponding states. J. Chem. Phys. 13:253–61 [Google Scholar]
  5. Levelt Sengers J. 2002. How Fluids Unmix Amsterdam: KNAW
  6. Rowlinson JS. 1988. Introductory essay. J.D. van der Waals: On the Continuity of the Gaseous and Liquid States JL Lebowitz 1–119 14 Stud. Stat. Mech. Amsterdam: North-Holland [Google Scholar]
  7. Domb C. 1996. The Critical Point Philadelphia: Taylor & Francis
  8. Zimm BH. 8.  1952. Shape of the coexistence curve in the critical region. J. Chem. Phys. 20:538 [Google Scholar]
  9. Rice OK. 9.  1955. Relation between isotherms and coexistence curve in the critical region. J. Chem. Phys. 23:169–73 [Google Scholar]
  10. Widom B, Rice OK. 10.  1955. Critical isotherm and the equation of state of liquid-vapor systems. J. Chem. Phys. 23:1250–55 [Google Scholar]
  11. Fisher ME. 11.  1959. Susceptibility of the plane Ising model. Physica 25:521–24 [Google Scholar]
  12. Kaufman B, Onsager L. 12.  1949. Crystal statistics. III. Short-range order in a binary Ising lattice. Phys. Rev. 76:1244–52 [Google Scholar]
  13. Essam JW, Fisher ME. 13.  1963. Pade approximant studies of the lattice gas and Ising ferromagnet below the critical point. J. Chem. Phys. 38:802–12 [Google Scholar]
  14. Domb C, Sykes MF. 14.  1957. On the susceptibility of a ferromagnetic above the Curie point. Proc. R. Soc. A 240:214–28 [Google Scholar]
  15. Widom B. 15.  1964. The degree of the critical isotherm. J. Chem. Phys. 41:1633–34 [Google Scholar]
  16. Widom B. 16.  1965. Equation of state in the neighborhood of the critical point. J. Chem. Phys. 43:3898–905 [Google Scholar]
  17. Fisher ME, Orkoulas G. 17.  2000. The Yang-Yang anomaly in fluid criticality: experiment and scaling theory. Phys. Rev. Lett. 85:696–99 [Google Scholar]
  18. Widom B. 18.  1965. Surface tension and molecular correlations near the critical point. J. Chem. Phys. 43:3892–97 [Google Scholar]
  19. Widom B, Rowlinson JS. 19.  1970. New model for the study of liquid-vapor phase transitions. J. Chem. Phys. 52:1670–84 [Google Scholar]
  20. Hammersley JM, Lewis JWE, Rowlinson JS. 20.  1975. Relationships between the multinomial and Poisson models of stochastic processes, and between the canonical and grand canonical ensembles in statistical mechanics, with illustrations and Monte Carlo methods for the penetrable sphere model of liquid-vapour equilibrium. Sankhyā: Indian J. Stat. A 37:457–91 [Google Scholar]
  21. Ruelle D. 21.  1971. Existence of a phase transition in a continuous classical system. Phys. Rev. Lett. 27:1040–41 [Google Scholar]
  22. Lebowitz JL, Lieb EH. 22.  1972. Phase transition in a continuum classical system with finite interactions. Phys. Lett. 39A:98–100 [Google Scholar]
  23. Griffiths RB, Widom B. 23.  1973. Multicomponent-fluid tricritical points. Phys. Rev. A 8:2173–75 [Google Scholar]
  24. Rudd DeFP, Widom B. 24.  1960. The critical solution phenomenon in two-component liquid systems. The system water-ethylene glycol mono-isobutyl ether. J. Chem. Phys. 33:1816–19 [Google Scholar]
  25. Zollweg JA. 25.  1971. Shape of the coexistence curve near a plait point in a three-component system. J. Chem. Phys. 55:1430–35 [Google Scholar]
  26. Lang JC Jr, Widom B. 26.  1975. Equilibrium of three liquid phases and approach to the tricritical point in benzene-ethanol-water-ammonium sulfate mixtures. Physica 81A:190–213 [Google Scholar]
  27. Bocko P. 27.  1980. The equilibrium of three liquid phases upon approach to the tricritical point in water–acetonitrile–benzene–n-hexane mixtures. Physica 103A:140–71 [Google Scholar]
  28. Sundar G, Widom B. 28.  1988. Three-phase equilibrium in solutions of polystyrene homologues in cyclohexane. Fluid Phase Equilibria 40:289–303 [Google Scholar]
  29. Widom B. 29.  1957. Inelastic molecular collisions with a Maxwellian interaction energy. J. Chem. Phys. 27:940–52 [Google Scholar]
  30. Drauglis E, Widom B. 30.  1958. Characteristic exponent for the radial wave equation with a Maxwellian potential. J. Chem. Phys. 28:309–10 [Google Scholar]
  31. Widom B. 31.  1960. Rotational relaxation of rough spheres. J. Chem. Phys. 32:913–23 [Google Scholar]
  32. Widom B. 32.  1971. Reaction kinetics in stochastic models. J. Chem. Phys. 55:44–52 [Google Scholar]
  33. Bartis JT, Widom B. 33.  1974. Stochastic models of the interconversion of three or more chemical species. J. Chem. Phys. 60:3474–82 [Google Scholar]
  34. Widom B. 34.  1963. Some topics in the theory of fluids. J. Chem. Phys. 39:2808–12 [Google Scholar]
  35. McMillan WG, Mayer JE. 35.  1945. The statistical thermodynamics of multicomponent systems. J. Chem. Phys. 13:276–305 [Google Scholar]
  36. Longuet-Higgins HC, Widom B. 36.  1964. A rigid sphere model for the melting of argon. Mol. Phys. 8:549–56 [Google Scholar]
  37. Widom B. 37.  1966. Random sequential addition of hard spheres to a volume. J. Chem. Phys. 44:3888–94 [Google Scholar]
  38. Rényi A. 38.  1958. On a one-dimensional problem concerning random space filling. Publ. Math. Inst. Hung. Acad. Sci. 3:109–27 1963. Sel. Transl. Math. Stat. Prob. 4:203–17 (English transl.) [Google Scholar]
  39. Widom B. 39.  1973. Random sequential filling of intervals on a line. J. Chem. Phys. 58:4043–44 [Google Scholar]
  40. Flory PJ. 40.  1939. Intramolecular reaction between neighboring substituents of vinyl polymers. J. Am. Chem. Soc. 61:1518–21 [Google Scholar]
  41. Fisher ME, Widom B. 41.  1969. Decay of correlations in linear systems. J. Chem. Phys. 50:3756–72 [Google Scholar]
  42. Cahn JW. 42.  1977. Critical point wetting. J. Chem. Phys. 66:3667–72 [Google Scholar]
  43. Ebner C, Saam WF. 43.  1977. New phase-transition phenomena in thin argon films. Phys. Rev. Lett. 38:1486–89 [Google Scholar]
  44. Kerins J, Widom B. 44.  1982. Line of contact of three fluid phases. J. Chem. Phys. 77:2061–70 [Google Scholar]
  45. Widom B, Widom H. 45.  1991. Model for line tension in three-phase equilibrium. Physica A 173:72–110 [Google Scholar]
  46. Szleifer I, Widom B. 46.  1992. Surface tension, line tension, and wetting. Mol. Phys. 75:925–43 [Google Scholar]
  47. Perković S, Szleifer I, Widom B. 47.  1993. Structure and tension of the boundary between surface phases. Mol. Phys. 80:729–39 [Google Scholar]
  48. Perković S, Blokhuis EM, Tessler E, Widom B. 48.  1995. Boundary tension: from wetting transition to prewetting critical point. J. Chem. Phys. 102:7584–94 [Google Scholar]
  49. Koga K, Widom B. 49.  2007. Line and boundary tension on approach to the wetting transition. J. Chem. Phys. 127:064704 [Google Scholar]
  50. Koga K, Indekeu JO, Widom B. 50.  2010. Infinite-order transitions in density-functional models of wetting. Phys. Rev. Lett. 104:036101 [Google Scholar]
  51. van der Waals JD. 51.  1894. Thermodynamische Theorie der Kapillarität unter voraussetzung stetiger Dichteänderung. Z. Phys. Chem. 13:657–725 1979. J. Stat. Phys. 20:197–244 (English transl., JS Rowlinson) [Google Scholar]
  52. Bukman DJ, Kolomeisky AB, Widom B. 52.  1997. Fluctuations in the structure of interfaces. Colloids Surf. A 128:119–28 [Google Scholar]
  53. Bukman DJ, Widom B. 53.  1998. Fluctuations in the structure of three-phase lines. Physica A 251:27–39 [Google Scholar]
  54. Djikaev Y, Widom B. 54.  2004. Geometric view of the thermodynamics of adsorption at a line of three-phase contact. J. Chem. Phys. 121:5602–10 [Google Scholar]
  55. Taylor CM, Widom B. 55.  2005. Adsorption equation for the line of three-phase contact. Mol. Phys. 103:647–55 [Google Scholar]
  56. Koga K, Widom B. 56.  2006. Line adsorption in a mean-field density-functional model. Mol. Phys. 104:3469–77 [Google Scholar]
  57. Rowlinson JS, Widom B. 1982. Molecular Theory of Capillarity Oxford: Oxford Univ. Press
  58. Sundar G, Widom B. 58.  1987. Interfacial tensions on approach to a tricritical point. J. Phys. Chem. 91:4802–9 [Google Scholar]
  59. Nagarajan N, Webb WW, Widom B. 59.  1982. Surface tension of a two-component liquid mixture near its critical solution point. J. Chem. Phys. 77:5771–83 [Google Scholar]
  60. Xia KQ, Franck CP, Widom B. 60.  1992. Interfacial tensions of phase-separated polymer solutions. J. Chem. Phys. 97:1446–54 [Google Scholar]
  61. Szleifer I, Widom B. 61.  1989. Structure and tension of the interface between dilute polymer solutions. J. Chem. Phys. 90:7524–34 [Google Scholar]
  62. De Gregorio P, Widom B. 62.  2007. Effect of solutes on the structure and energetics of a model solvent. J. Phys. Chem. C 111:16060–69 [Google Scholar]
  63. De Gregorio P, Toledo JC, Widom B. 63.  2008. Long tail correlations between hydrophobic solutes in a model solvent. Mol. Phys. 106:419–31 [Google Scholar]
  64. Barbosa MAA, Widom B. 64.  2010. Molecular correlations and solvation in simple fluids. J. Chem. Phys. 132:214506 [Google Scholar]
  65. Evans R, Leote de Carvalho RJF, Henderson JR, Hoyle DC. 65.  1994. Asymptotic decay of correlations in liquids and their mixtures. J. Chem. Phys. 100:591 [Google Scholar]
  66. Houston PL. 2001. Chemical Kinetics and Reaction Dynamics New York: McGraw-Hill
  67. Widom B. 2002. Statistical Mechanics: A Concise Introduction for Chemists Cambridge, UK: Cambridge Univ. Press
  68. Widom B. 68.  2009. Scaling laws. Scholarpedia 4:109054 [Google Scholar]
  69. Widom B. 1997. Thermodynamics, Equilibrium. . In the Encyclopedia of Applied Physics GL Trigg 21281–310 New York: Wiley [Google Scholar]
  70. Griffiths RB, Wheeler JC. 70.  1970. Critical points in multicomponent systems. Phys. Rev. A 2:1047–64 [Google Scholar]
  71. Wilson KG. 71.  1971. Renormalization group and critical phenomena. I. Renormalization group and the Kadanoff scaling picture. Phys. Rev. B 4:3174–83 [Google Scholar]
  72. Wilson KG.72.  1971. Renormalization group and critical phenomena. II. Phase-space cell analysis of critical behavior. Phys. Rev. B 4:3184–205 [Google Scholar]
  73. Niemeijer Th, van Leeuwen JMJ. 73.  1973. Wilson theory for spin systems on a triangular lattice. Phys. Rev. Lett. 31:1411–14 [Google Scholar]
  74. van Leeuwen JMJ. 74.  1984. Real space renormalization for fluids and interfaces. Lect. Notes Phys. 206:56–79 [Google Scholar]
  75. Widom B. 75.  1986. Lattice model of microemulsions. J. Chem. Phys. 84:6943–54 [Google Scholar]
  76. Dawson KA, Lipkin MD, Widom B. 76.  1986. Hamiltonian and phenomenological models of microemulsions. Physica A 140:26–34 [Google Scholar]
  77. Widom B. 77.  1987. Phase transitions in surfactant solutions and in their interfaces. Langmuir 3:12–17 [Google Scholar]
  78. Rubinstein M. 78.  1987. Discretized model of entangled-polymer dynamics. Phys. Rev. Lett. 59:1946–49 [Google Scholar]
  79. Duke TA. 79.  1989. Tube model of field-inversion electrophoresis. Phys. Rev. Lett. 62:2877–80 [Google Scholar]
  80. Widom B, Viovy JL, Défontaines AD. 80.  1991. Repton model of gel electrophoresis and diffusion. J. Phys. I 1:1759–84 [Google Scholar]
  81. Kolomeisky AB, Widom B. 81.  1998. A simplified “ratchet” model of molecular motors. J. Stat. Phys. 93:633–45 [Google Scholar]

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