The formalism of density functional theory (DFT) with Perdew and Wang exchange-correlation functional, has been employed to study the electronic and geometric structures of silver cation and the neutral dimer bonded with carbon monoxide and oxygen. A charge state study of the use of [Formula: see text] and Ag 2, for the catalytic oxidation of CO , has been performed and compared with our previous results for [Formula: see text]. Different possible structures for [Formula: see text], Ag 2 CO +, Ag 2 O 2 and Ag 2 CO have been investigated in detail. An all electron 6-311 ++ G ** basis set for carbon and oxygen, and a pseudopotential basis set for silver have been used for performing the calculations. Using silver cation and neutral dimer as catalysts, full catalytic cycles producing two carbon dioxide molecules have been presented. Also, the presence of intermediate states, [Formula: see text] and Ag 2 CO 3, which can be detected experimentally, are predicted. The presence of an energy barrier for certain reactions from the catalytic cycle have been observed. This is noteworthy since no reaction barrier has been observed using silver anion dimer as a catalyst, for the same catalytic cycle. Analyzing the charge state effects, it is concluded that silver anion dimer performs better as a catalyst, compared with silver cation and neutral dimers.
Density functional studies of the catalytic oxidation of CO using small aurocarbons
