The weighted correlation approach for density functional theory: a study on the structure of the electric double layer
2011 (English)In: Journal of Physics: Condensed Matter, ISSN 0953-8984, E-ISSN 1361-648X, Vol. 23, no 17, 175002- p.Article in journal (Refereed) Published
Within the framework of density functional theory, a weighted correlation approach is developed in order to obtain the density distributions of an inhomogeneous fluid. It results in a formally exact expression, by means of the concept of a weighted pair correlation function, used to evaluate the change of the single-particle direct correlation function of the system relative to that of a reference state. When applying the approach for practical use, however, an approximation of the pair correlation function has to be made, along with an appropriate definition of a weight function. Noticeably, combining this approach with fundamental measure theory gives rise to a new method, which we call the FMT/WCA-k(2) approach, for studying the structural and thermodynamic properties of a charged hard-sphere fluid subjected to a spatially varying external potential. Application of the FMT/WCA-k(2) approach in a range of electrolyte concentrations and surface charge densities, against the Monte Carlo simulations, shows that it is superior to the typical approaches of density functional theory in predicting the ionic density profiles of both counter-ions and co-ions near a highly charged surface. It is capable of capturing the fine features of the structural properties of the electric double layers, to well reproduce the layering effect and the charge inversion phenomenon, also in strongly coupled cases where divalent counter-ions are involved. In addition, it is found that the FMT/WCA-k(2) approach even has an advantage over the anisotropic, hyper-netted chain approaches in giving better agreement with the Monte Carlo results.
Place, publisher, year, edition, pages
2011. Vol. 23, no 17, 175002- p.
IdentifiersURN: urn:nbn:se:kth:diva-33218DOI: 10.1088/0953-8984/23/17/175002ISI: 000289555700004ScopusID: 2-s2.0-79955033089OAI: oai:DiVA.org:kth-33218DiVA: diva2:419825
FunderICT - The Next Generation
QC 201105302011-05-302011-05-022013-04-09Bibliographically approved