Toward Accurate Adsorption Energetics on Clay Surfaces

摘要: Clay minerals are ubiquitous in nature, and the manner which they interact with their surroundings has important industrial environmental implications. Consequently, a molecular-level understanding of adsorption molecules on clay surfaces is crucial. In this regard computer simulations play an role, yet accuracy widely used empirical force fields (FF) density functional theory (DFT) exchange-correlation functionals often unclear systems dominated by weak interactions. Herein we present results from quantum Monte Carlo (QMC) for water methanol prototypical kaolinite. To best our knowledge, first time QMC been to investigate at complex, natural surface such as clay. As well being valuable own right, benchmarks obtained provide reference data against performance cheaper DFT methods can be tested. Indeed using various yields very broad range energies, it priori evaluation better. reveals that considered here essential account van der Waals (vdW) dispersion forces since alters both absolute relative energies methanol. We show, via FF simulations, incorrect lead significant changes interfacial densities solutions kaolinite interface. Despite clear improvements offered vdW-corrected vdW-inclusive functionals, overestimated, suggesting treatment vdW not solved problem.