DOUBLE-LAYER INTERACTIONS IN MONOVALENT AND DIVALENT ELECTROLYTES - A COMPARISON OF THE ANISOTROPIC HYPERNETTED CHAIN THEORY AND MONTE-CARLO SIMULATIONS

被引:199
作者
KJELLANDER, R
AKESSON, T
JONSSON, B
MARCELJA, S
机构
[1] CHEM CTR LUND,S-22100 LUND,SWEDEN
[2] AUSTRALIAN NATL UNIV,RES SCH PHYS SCI,DEPT APPL MATH,CANBERRA,ACT 2601,AUSTRALIA
关键词
D O I
10.1063/1.463218
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
The interaction between charged surfaces in 1:1, 1:2, and 2:2 electrolyte solutions at various concentrations have been calculated using the anisotropic hypernetted chain (HNC) theory and Monte Carlo (MC) simulations. For divalent counterions, the surface interaction has an attractive minimum at short separations. This minimum turns more attractive at increasing electrolyte concentration, while the interaction at somewhat larger separations becomes oscillatory. The agreement between the HNC and the MC results is excellent for the 1:2 and 2:2 electrolyte systems. For 1:1 electrolytes the surface interaction is repulsive except at high concentrations at which it shows a weak attractive minimum. The HNC and the MC results agree quantitatively except in a few angstroms wide region at short separations, where the agreement is only qualitative due to a slight difference in the contributions from the hard core interactions. This is a consequence of the neglect of the short-range bridge function in the HNC approximation.
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页码:1424 / 1431
页数:8
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