Studying the adsorption of emerging organic contaminants in zeolites with dispersion‐corrected density functional theory calculations: From numbers to recommendations

Abstract Adsorption energies obtained from dispersion‐corrected density functional theory (DFT) calculations show a considerable dependence on the choice of exchange‐correlation functional and dispersion correction. A number of investigations have employed different approaches to compute adsorption energies of small molecules in zeolites, using reference values from high‐level calculations and/or experiments. Such comparative studies are lacking for larger functional organic molecules such as pharmaceuticals or personal care products, despite their potential relevance for applications, e. g ., in contaminant removal or drug delivery. The present study aims to fill this gap by comparing adsorption energies and, for selected cases, equilibrium structures of emerging organic contaminants adsorbed in MOR‐ and FAU‐type all‐silica zeolites. A total of 13 dispersion‐corrected DFT approaches are compared, including methods using a pairwise dispersion correction as well as non‐local van der Waals density functionals. While absolute values of adsorption energies vary widely, qualitative trends across the set of zeolite‐guest combinations are not strongly dependent on the choice of functional. For selected cluster models, DFT adsorption energies are compared to reference values from coupled cluster (DLPNO‐CCSD(T)) calculations. Although all DFT approaches deliver systematically more negative adsorption energies than the coupled cluster reference, this tendency is least pronounced for the rev‐vdW‐DF2 functional.