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The first three coefficients in the high temperature series expansion of free energy for simple potential models with hard-sphere cores and continuous tails

Abstract: The first three coefficients of the high temperature series expansion (HTSE) of the Helmholtz free energy for a number of simple potential models with hard-sphere cores plus continuous tails are obtained for the first time from Monte Carlo simulations. The potential models considered include Square-well, Sutherland, attractive Yukawa, and triangle-well with different potential ranges, as well as a model potential qualitatively resembling the depletion potential in colloidal dispersions. The simulation data are used to evaluate performance of a recent coupling parameter series expansion (CPSE) in calculating for these coefficients, and a traditional macroscopic compressibility approximation (MCA) for the second-order coefficient only. A comprehensive comparison based on these coefficients from the two theoretical approaches and simulations enables one to conclude that (i) unlike one common experience that the widely used MCA usually underestimates the second-order coefficient, the MCA can both overestimate and underestimate the second-order coefficient, and worsens as the range of the potential decreases; and (ii) in contrast, the CPSE not only reproduce the trends in the density dependence of the perturbation coefficients, even the third one, observed in the simulations, but also the agreement is quantitative in most cases, and this clearly highlights the potential of the CPSE in providing accurate estimations for the higher-order coefficients, thus giving rise to an accurate higher-order HTSE.

 Autoría: Zhou S., Solana J.,

 Fuente: Journal of physical chemistry B, 2013, 117(31), 9305-9313

 Editorial: American Chemical Society

 Fecha de publicación: 11/07/2013

 Nº de páginas: 9

 Tipo de publicación: Artículo de Revista

 DOI: 10.1021/jp405406f

 ISSN: 1520-5207,1520-6106

 Proyecto español: FIS2009-09616

 Url de la publicación: https://doi.org/10.1021/jp405406f