Understanding the adsorption mechanisms of metal cations onto soils and sediments is of critical importance in the protection of the environment, especially for the case of radioactive materials including the fission product Cs-137. Mechanism-based adsorption models for the long-term interaction of chemical and radionuclide species with clay minerals are needed to improve the accuracy of groundwater reaction and flow models, as well as related simulations for performance assessment of waste sites and repositories. Toward this goal, molecular simulation using geometry optimization and molecular dynamics methods have been used to investigate the adsorption behavior of Cs+ and Rb+ cations at frayed edge wedges (a proxy for frayed edge sites, FES) and in the interlayer region formed as a result of the transformation of muscovite to Al-hydroxy interlayered vermiculite (HIV) during weathering and pedogenesis. Frayed edge wedges, formed both on individual smectite and illite phases and on the mica-HIV intergrade, have previously been recognized as significant sinks for the strong adsorption of Cs+ and Rb+. Atomic density profiles, interlayer adsorption site maps, radial distribution functions, and adsorption enthalpies derived from the equilibrated structural models are used to evaluate the optimal adsorption configurations and thermodynamics for Cs- and Rb-endmembers, a 50:50 Cs-Rb composition for the aqueous interlayer of vermiculite, and for the interlayer wedge zone as mica is transformed to HIV (i.e., HIV-mica wedge). Adsorption enthalpies for both cations are significantly larger for the frayed edge wedges (as represented by the HIV-mica wedge model) compared to values for the vermiculite and mica interlayers. Cesium cation binds more strongly than Rb+ in the vermiculite interlayer, while Rb+ binds more strongly than Cs+ in the HIV-mica wedge. In all cases, the derived adsorption enthalpies for both cations indicate a preference for the wedge environment where electrostatic interaction is enhanced due to the presence of layer charge and the increased size of interlayer at the wedge accommodating cations larger than K+.