  Anion exchange at positively charged interfaces plays an important role in a
variety of physical and chemical processes. However, the molecular scale
details of these processes, especially with heavy and large anionic complexes,
are not well-understood. We studied the adsorption of $PtCl_6^{2-}$ anionic
complexes to floating DPTAP monolayers in the presence of excess $Cl^-$ as a
function of the bulk chlorometalate concentration. In situ x-ray scattering and
fluorescence measurements, which are element and depth sensitive, show that the
chlorometalate ions only adsorb in the diffuse layer at lower concentrations,
while they adsorb predominantly in the Stern layer at higher concentrations.
The response of DPTAP molecules to the adsorbed ions is determined
independently by grazing incidence x-ray diffraction, and supports this
picture. Molecular dynamics simulations further elucidate the nanoscale
structure of the interfacial complexes. The results suggest that ion hydration
and ion-ion correlations play a key role in the competitive adsorption process.
