Reaction of NO with Groups IV and VI Transition Metal Oxide Clusters.

The addition of NO to Group IV (MO) and Group VI (MO) ( = 1-3) nanoclusters was studied using both density functional theory (DFT) and coupled cluster theory (CCSD(T)). The structures and overall binding energetics were predicted for Lewis acid-base addition without transfer of spin (a physisorption-type process) and the formation of either cluster-ONO (HONO-like or bidentate bonding) or NO formation where for both the spin is transferred to the metal oxide clusters (a chemisorption-type process). Only chemisorption of NO is predicted to be thermodynamically allowed at temperatures ≥298 K for Group IV (MO) clusters with the formation of surface chemisorbed NO being by far the most energetically favorable. The ligand binding energies (LBEs) for physisorption and chemisorption on the TiO nanoclusters are consistent with computational studies of the bulk solids. Chemisorption is only predicted to occur for (CrO) clusters in the form of a terminal nitrate containing species whereas the larger chemisorbed nitrate structures for (MoO) and (WO) were found to be metastable and unlikely to form in any appreciable amount at temperatures of 298 K and higher. NO is predicted to only be capable of physisorbing to (MoO) and (WO) at lower temperatures and therefore unlikely to bind NO at temperatures ≥298 K. Correlations between the (MO)NO ligand bond energies and the chemical properties of the parent (MO) clusters (Lewis acidity, ionization potentials, excitation energies, and M = O/M-O bond strengths) are described.