Adsorption of air pollutants onto silver and gold atomic clusters: DFT and PNO-LCCSD-F12 calculations

We provide a comprehensive investigation of intermolecular interactions between atmospheric gaseous pollutants, including CH₄, CO, CO₂, NO, NO₂, SO₂, as well as H₂O and Ag_n (n = 1-22) or Au_n (n = 1-20) atomic clusters. The optimized geometries of all the systems investigated in our study were determined using density functional theory (DFT) with M06-2X functional and SDD basis set. The PNO-LCCSD-F12/SDD method was used for more accurate single-point energy calculations. Compared to their isolated states, the structures of the Ag_n and Au_n clusters undergo severe deformations upon adsorption of the gaseous species, which become more significant as the size of the clusters decreases. Considering that, in addition to adsorption energy, we have determined the interaction and deformation energy of all the systems. All our calculations consistently show that among the gaseous species examined, SO₂ and NO₂ exhibit a higher preference for adsorption on both types of clusters, with a slightly higher preference for the Ag clusters compared to the Au clusters, with the SO₂/Ag₁₆ system exhibiting the lowest adsorption energy. The type of intermolecular interactions was investigated through wave function analyses, including natural bond orbital (NBO) and quantum theory of atoms in molecules (QTAIM), showing that NO₂ and SO₂ are chemisorbed on the Ag_n and Au_n atomic clusters, whereas the other gas molecules exhibit a much weaker interaction with them. The reported data can be used as input parameters for molecular dynamics simulations to study the selectivity of atomic clusters towards specific gases under ambient conditions, as well as to design materials that take advantage of the studied intermolecular interactions.