CO capture and conversion to HOCO radical by ionized water clusters.

The CO molecule can interact with the hydroxyl radical ((•)OH) via either a weak noncovalent interaction or strong covalent bonding. Upon the ionization of neutral water clusters, the resulting water cluster cations produce protonated water clusters and hydroxyl radicals. In this regard, we investigate the interactions of a CO molecule with water dimer and trimer cations using density functional theory (DFT), Möller-Plesset second-order perturbation theory (MP2), and coupled cluster theory with single, double, and perturbative triple excitations [CCSD(T)]. It is found that the reaction products of CO by the water dimer and trimer cations form a HOĊO radical solvated by a protonated water monomer and dimer, respectively. These radicals are useful intermediates to make oxalic acids, formic acids, metal ligands, and so on, which is important in green chemistry.