Density functional theory of the electrical double layer: the RFD functional

作者：Gillespie D^*; Valisko N; Boda D

来源：Journal of Physics: Condensed Matter , 2005, 17(42): 6609-6626.

DOI：10.1088/0953-8984/17/42/002

Density functional theory (DFT) of electrolytes is applied to the electrical double layer under a wide range of conditions. The ions are charged, hard spheres of different size and valence, and the wall creating the double layer is uncharged, weakly charged, and strongly charged. Under all conditions, the density and electrostatic potential profiles calculated using the recently proposed RFD electrostatic functional (Gillespie et al 2002 J. Phys.: Condens. Matter 14 12129; 2003 Phys. Rev. E 68 031503) compare well to Monte Carlo simulations. When the wall is strongly charged, the RFD functional results agree with the results of a simpler perturbative electrostatic DFT, but the two functionals' results qualitatively disagree when the wall is uncharged or weakly charged. The RFD functional reproduces these phenomena of weakly charged double layers. It also reproduces bulk thermodynamic quantities calculated from pair correlation functions.

• 出版日期2005-10-26