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Scaled-particle theory analysis of cylindrical cavities in solution
Phys. Rev. E 91, 042315 – Published 27 April, 2015
DOI: https://doi.org/10.1103/PhysRevE.91.042315
Abstract
The solvation of hard spherocylindrical solutes is analyzed within the context of scaled-particle theory, which takes the view that the free energy of solvating an empty cavitylike solute is equal to the pressure-volume work required to inflate a solute from nothing to the desired size and shape within the solvent. Based on our analysis, an end cap approximation is proposed to predict the solvation free energy as a function of the spherocylinder length from knowledge regarding only the solvent density in contact with a spherical solute. The framework developed is applied to extend Reiss's classic implementation of scaled-particle theory and a previously developed revised scaled-particle theory to spherocylindrical solutes. To test the theoretical descriptions developed, molecular simulations of the solvation of infinitely long cylindrical solutes are performed. In hard-sphere solvents classic scaled-particle theory is shown to provide a reasonably accurate description of the solvent contact correlation and resulting solvation free energy per unit length of cylinders, while the revised scaled-particle theory fitted to measured values of the contact correlation provides a quantitative free energy. Applied to the Lennard-Jones solvent at a state-point along the liquid-vapor coexistence curve, however, classic scaled-particle theory fails to correctly capture the dependence of the contact correlation. Revised scaled-particle theory, on the other hand, provides a quantitative description of cylinder solvation in the Lennard-Jones solvent with a fitted interfacial free energy in good agreement with that determined for purely spherical solutes. The breakdown of classical scaled-particle theory does not result from the failure of the end cap approximation, however, but is indicative of neglected higher-order curvature dependences on the solvation free energy.
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References (44)
- H. Reiss, H. L. Frisch, and J. L. Lebowitz, J. Chem. Phys. 31, 369 (1959).
- H. Reiss, H. L. Frisch, E. Helfand, and J. L. Lebowitz, J. Chem. Phys. 32, 119 (1960).
- H. Reiss, in Advances in Chemical Physics, edited by I. Prigogine (John Wiley & Sons, Inc., Hoboken, NJ, 1965), p. 1.
- R. A. Pierotti, J. Phys. Chem. 69, 281 (1965).
- R. A. Pierotti, Chem. Rev. 76, 717 (1975).
- A. Ben-Naim and H. L. Friedman, J. Phys. Chem. 71, 448 (1967).
- F. H. Stillinger, J. Solut. Chem. 2, 141 (1973).
- J. R. Henderson, J. Chem. Phys. 116, 5039 (2002).
- J. R. Henderson and F. van Swol, J. Chem. Phys. 89, 5010 (1988).
- F. M. Floris, J. Phys. Chem. B 108, 16244 (2004).
- H. S. Ashbaugh and T. M. Truskett, J. Chem. Phys. 134, 014507 (2011).
- H. S. Ashbaugh and L. R. Pratt, Rev. Mod. Phys. 78, 159 (2006).
- J. R. Dowdle, S. V. Buldyrev, H. E. Stanley, P. G. Debenedetti, and P. J. Rossky, J. Chem. Phys. 138, 064506 (2013).
- H. S. Ashbaugh, J. Chem. Phys. 130, 204517 (2009).
- H. S. Ashbaugh and L. R. Pratt, J. Phys. Chem. B 111, 9330 (2007).
- H. S. Ashbaugh, Chem. Phys. Lett. 477, 109 (2009).
- R. M. Gibbons, Mol. Phys. 17, 81 (1969).
- R. M. Gibbons, Mol. Phys. 18, 809 (1970).
- J. A. Barker and J. R. Henderson, Rev. Mod. Phys. 48, 587 (1976).
- G. Lasher, J. Chem. Phys. 53, 4141 (1970).
- M. A. Cotter, Phys. Rev. A 10, 625 (1974).
- A. G. Ogston, Trans. Faraday Soc. 54, 1754 (1958).
- L. R. Pratt and A. Pohorille, Proc. Natl. Acad. Sci. USA 89, 2995 (1992).
- A. Jain and H. S. Ashbaugh, J. Chem. Phys. 129, 174505 (2008).
- G. Graziano, J. Phys. Chem. B 113, 11232 (2009).
- G. Graziano, Chem. Phys. Lett. 440, 221 (2007).
- H. Hadwiger, Vorlesungen über Inhalt, Oberfläche, und Isoperimetrie (Springer, Berlin, 1957).
- P. M. Konig, R. Roth, and K. R. Mecke, Phys. Rev. Lett. 93, 160601 (2004).
- R. Roth, Y. Harano, and M. Kinoshita, Phys. Rev. Lett. 97, 078101 (2006).
- B. B. Laird, A. Hunter, and R. L. Davidchack, Phys. Rev. E 86, 060602 (2012).
- F. Sedlmeier and R. R. Netz, J. Chem. Phys. 137, 135102 (2012).
- H. Hansen-Goos and R. Roth, J. Phys.: Condens. Matter 18, 8413 (2006).
- Z. H. Jin, J. Kim, and J. Z. Wu, Langmuir 28, 6997 (2012).
- S. M. Oversteegen and R. Roth, J. Chem. Phys. 122, 214502 (2005).
- D. W. Siderius and D. S. Corti, Phys. Rev. E 71, 036141 (2005).
- D. W. Siderius and D. S. Corti, Phys. Rev. E 75, 011108 (2007).
- T. M. Reed and K. E. Gubbins, Applied Statisitcal Mechanics: Thermodynamics and Transport Properties of Fluids (Butterworth-Heinmann, Boston, 1973).
- C. Benzi, M. Xossi, R. Improta, and V. Barone, J. Comput. Chem. 26, 1096 (2005).
- D. Frenkel and B. Smit, Understanding Molecular Simulation: From Algorithms to Applications, 2nd ed. (Academic, San Diego, 2001).
- J. K. Percus, J. Stat. Phys. 15, 423 (1976).
- G. Hummer, S. Garde, A. E. Garcia, M. E. Paulaitis, and L. R. Pratt, J. Phys. Chem. B 102, 10469 (1998).
- J. R. Henderson and F. van Swol, Mol. Phys. 51, 991 (1984).
- P. Attard and G. A. Moule, Mol. Phys. 78, 943 (1993).
- M. Heying and D. S. Corti, Mol. Phys. 112, 2160 (2014).