Effective screening length and quasiuniversality for the restricted primitive model of an electrolyte solution

被引:16
作者
Janecek, Jiri [1 ]
Netz, Roland R. [2 ]
机构
[1] Brno Univ Technol, Inst Phys & Appl Chem, Brno 61200, Czech Republic
[2] Tech Univ Munich, Dept Phys, D-85748 Garching, Germany
关键词
Debye-Huckel theory; electrolytes; Monte Carlo methods; osmosis; thermodynamic properties; MONTE-CARLO SIMULATIONS; CHARGED HARD-SPHERES; DRESSED-ION THEORY; MEAN SPHERICAL APPROXIMATION; INTEGRAL-EQUATION THEORY; FLUID-SOLID EQUILIBRIUM; FREE-ENERGY; ASYMMETRIC ELECTROLYTES; COLLOIDAL SUSPENSIONS; DIFFERENT DIAMETERS;
D O I
10.1063/1.3058777
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Monte Carlo simulations for the restricted primitive model of an electrolyte solution above the critical temperature are performed at a wide range of concentrations and temperatures. Thermodynamic properties such as internal energy, osmotic coefficient, activity coefficient, as well as spatial correlation functions are determined. These observables are used to investigate whether quasiuniversality in terms of an effective screening length exists, similar to the role played by the effective electron mass in solid-state physics. To that end, an effective screening length is extracted from the asymptotic behavior of the Fourier-transformed charge-correlation function and plugged into the Debye-Huckel limiting expressions for various thermodynamic properties. Comparison with numerical results is favorable, suggesting that correlation and other effects not captured on the Debye-Huckel limiting level can be successfully incorporated by a single effective parameter while keeping the functional form of Debye-Huckel expressions. We also compare different methods to determine mean ionic activity coefficient in molecular simulations and check the internal consistency of the numerical data.
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页数:15
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