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Swelling clay minerals control the hydrologic and mechanical properties of many soils, sediments, and sedimentary rocks. This important and well-known phenomenon remains challenging to predict because it emerges from complex multiscale couplings between aqueous chemistry and colloidal interaction mechanics in nanoporous clay assemblages, for which predictive models remain elusive. In particular, the predominant theory of colloidal interactions across fluid films, the widely used Derjaguin− Landau−Verwey−Overbeek model, fails to predict the ubiquitous existence of stable swelling states at interparticle distances below 3 nm that are stabilized by specific inter-atomic interactions in overlapping electrical double layers between the charged clay surfaces. Atomistic simulations have the potential to generate detailed insights into the mechanisms of these interactions. Recently, we developed a metadynamics-based molecular dynamics simulation methodology that can predict the free energy of interaction between parallel smectite clay particles in a wide range of interparticle distances (from 0.3 to 3 nm) and salinities (from 0.0 to 1.0 M NaCl). Here, we extend this work by characterizing the sensitivity of interparticle interactions to counterion type (Na, K, Ca). We establish a detailed picture of the free energy of interaction of parallel clay particles across water films as the sum of five interaction mechanisms with different sensitivities to salinity, counterion type, and interparticle distance.

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