The behavior of self-assembled monolayers of thiohexadecanoic acid adsorbed
onto gold interacting in asymmetric 2:1 electrolytes has been studied with
direct force measurements. The effects of two divalent cations (Mg2+ and C
a2+) were studied at concentrations ranging from 1 mu M to 10 mM. As compar
ed to interactions in the presence of Na+, the divalent ions adsorb strongl
y to the surfaces, with the effect of lowering the surface potential and de
creasing the double-layer repulsion. At concentrations above 10 mu M, the C
a2+ ions were found to adsorb stronger than Mg2+. Ca2+ ions cause charge re
versal at high concentrations, and the net interactions at 10 mM were attra
ctive over the measurable range. (C) 2000 Academic Press.