The capacitance of the solvent primitive model double layer at low effective temperatures

被引:35
作者
Boda, D
Henderson, D
机构
[1] Univ Veszprem, Dept Phys Chem, H-8201 Veszprem, Hungary
[2] Brigham Young Univ, Dept Chem & Biochem, Provo, UT 84602 USA
关键词
D O I
10.1063/1.481507
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 effect of the solvent, modeled as a hard sphere fluid, on the behavior of the double layer at low temperatures is studied by means of Monte Carlo simulations. We find that the density profiles are strongly affected by the addition of solvent molecules. The profiles pass from near monotonic functions that exhibit partial drying to oscillatory functions that exhibit partial wetting as the bulk density of the solvent is increased in the system. However, the capacitance, as in the case of the primitive model, increases at low effective temperatures, while after a maximum it decreases at higher effective temperatures as the temperature increases. We find that the adsorption of the ions decreases and changes sign from positive to negative with the decreasing temperature at low electrode charges. Some of these features can be explained by means of a contact value theorem. (C) 2000 American Institute of Physics. [S0021-9606(00)51920-5].
引用
收藏
页码:8934 / 8938
页数:5
相关论文
共 30 条
[11]   THE DOUBLE-LAYER OF SINGLE-CRYSTAL GOLD ELECTRODES IN LIQUID AND SOLID HCLO4.5.5H2O [J].
HAMELIN, A ;
ROTTGERMANN, S ;
SCHMICKLER, W .
JOURNAL OF ELECTROANALYTICAL CHEMISTRY, 1987, 230 (1-2) :281-287
[12]   ANOMALOUS ADSORPTION OF IONS AT AN ELECTRODE [J].
HENDERSON, D ;
BAROJAS, J ;
BLUM, L .
JOURNAL OF PHYSICAL CHEMISTRY, 1983, 87 (22) :4544-4547
[13]   A SIMPLE THEORY FOR THE FORCE BETWEEN SPHERES IMMERSED IN A FLUID [J].
HENDERSON, D ;
LOZADACASSOU, M .
JOURNAL OF COLLOID AND INTERFACE SCIENCE, 1986, 114 (01) :180-183
[14]   EXACT FORMULA FOR THE CONTACT VALUE OF THE DENSITY PROFILE OF A SYSTEM OF CHARGED HARD-SPHERES NEAR A CHARGED WALL [J].
HENDERSON, D ;
BLUM, L ;
LEBOWITZ, JL .
JOURNAL OF ELECTROANALYTICAL CHEMISTRY, 1979, 102 (03) :315-319
[15]   STUDIES IN STATISTICAL-MECHANICS OF COULOMBIC SYSTEMS .2. ERGODIC PROBLEMS IN MONTE-CARLO SIMULATIONS OF RESTRICTED PRIMITIVE MODEL [J].
LARSEN, B ;
ROGDE, SA .
JOURNAL OF CHEMICAL PHYSICS, 1978, 68 (03) :1309-1311
[16]   CAPACITANCE OF METAL MOLTEN-SALT INTERFACES [J].
PAINTER, KR ;
BALLONE, P ;
TOSI, MP ;
GROUT, PJ ;
MARCH, NH .
SURFACE SCIENCE, 1983, 133 (01) :89-100
[17]   Structure of electric double layers: A simple weighted density functional approach [J].
Patra, CN .
JOURNAL OF CHEMICAL PHYSICS, 1999, 111 (21) :9832-9838
[18]   PAIR CORRELATION-FUNCTIONS AND DENSITY PROFILES IN THE PRIMITIVE MODEL OF THE ELECTRIC DOUBLE-LAYER [J].
PLISCHKE, M ;
HENDERSON, D .
JOURNAL OF CHEMICAL PHYSICS, 1988, 88 (04) :2712-2718
[19]   The hypernetted chain (HNC) equation for higher valence electrolytes [J].
Rasaiah, J. .
CHEMICAL PHYSICS LETTERS, 1970, 7 (02) :260-264
[20]   INTEGRAL EQUATION COMPUTATIONS FOR AQUEOUS 1-1 ELECTROLYTES . ACCURACY OF METHOD [J].
RASAIAH, JC ;
FRIEDMAN, HL .
JOURNAL OF CHEMICAL PHYSICS, 1969, 50 (09) :3965-&