Reduced density profile of small particles near a large particle: Results of an integral equation theory with an accurate bridge function and a Monte Carlo simulation

• Published in: The Journal of chemical physics 2019-07, Vol.151 (4), p.044506-044506
• Main Authors: Nakamura, Yuka, Arai, Shota, Kinoshita, Masahiro, Yoshimori, Akira, Akiyama, Ryo
• Format: Article
• Language: English
• Subjects: Closures; Computer simulation; Density; Integral equations; Mathematical analysis; Monte Carlo simulation; Solvents
• ISSN: 0021-9606; 1089-7690
• DOI: 10.1063/1.5100040

Solute–solvent reduced density profiles of hard-sphere fluids were calculated by using several integral equation theories for liquids. The traditional closures, Percus–Yevick (PY) and the hypernetted-chain (HNC) closures, as well as the theories with bridge functions, Verlet, Duh–Henderson, and Kinoshita (named MHNC), were used for the calculation. In this paper, a one-solute hard-sphere was immersed in a one-component hard-sphere solvent and various size ratios were examined. The profiles between the solute and solvent particles were compared with those calculated by Monte Carlo simulations. The profiles given by the integral equations with the bridge functions were much more accurate than those calculated by conventional integral equation theories, such as the Ornstein–Zernike (OZ) equation with the PY closure. The accuracy of the MHNC–OZ theory was maintained even when the particle size ratio of solute to solvent was 50. For example, the contact values were 5.7 (Monte Carlo), 5.6 (MHNC), 7.8 (HNC), and 4.5 (PY), and the first minimum values were 0.48 (Monte Carlo), 0.46 (MHNC), 0.54 (HNC), and 0.40 (PY) when the packing fraction of the hard-sphere solvent was 0.38 and the size ratio was 50. The asymptotic decay and the oscillation period for MHNC–OZ were also very accurate, although those given by the HNC–OZ theory were somewhat faster than those obtained by Monte Carlo simulations.