CO2 adsorption and activation on Ag(1 1 1) surfaces in the presence of surface charge density: A static gas phase DFT study.

[Display omitted] • DFT and DFTB models mimic surface plasmon effects of localize extra charge density. • DFT ground model is able to predict *CO 2 δ− formation over pristine Ag(1 1 1) surface. • A second CO 2 adsorption forms *2CO 2 δ− activated species, weakening the C O bonds. The CO 2 reduction reaction on Ag in the presence of surface plasmons are of strong interest in photocatalysis. Here, two Density Functional Theory (DFT) approaches are proposed to localize charges at the Ag surface to mimic surface plasmon excitation. These calculations predict charge localization at the outermost surface layer, a result confirmed via light excitation at the plasmon resonance modeled by Density Functional Tight Binding Hamiltonian (DFTB) theory. The CO 2 (gas) reduction initial steps are studied by DFT models showing that bonded species can be created on top of an Ag-atom in the presence of extra charges. A second CO 2 molecule can assist the first molecule, decreasing the charge carrier density requirement for CO 2 reduction bonded species. A Molecular Dynamics (MD) study shows a possible interaction among CO 2 molecule. These results show that a static DFT simulation can mimic charge localization resulting from surface plasmon effects, thus enabling studies on surface plasmon-enhanced chemical reactions, paving the way for future time-dependent (TD) studies. [ABSTRACT FROM AUTHOR]