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.

Reaction of CO with Groups 4 and 6 Transition Metal Oxide Clusters.

Density functional theory (DFT) and coupled cluster theory (CCSD(T)) were used to study the addition of CO to group 4 (MO) and group 6 (MO) (n = 1, 2, 3) nanoclusters. The structures and energetics arising from Lewis acid-base addition (physisorption) and formation of CO (chemisorption) of CO to these clusters were predicted. Physisorption and chemisorption of CO are predicted to be thermodynamically allowed for group 4 (MO) clusters, with chemisorption being more favored energetically.

Reaction of CO with UO Nanoclusters.

Adsorption of CO to uranium oxide, (UO), clusters was modeled using density functional theory (DFT) and coupled cluster theory (CCSD(T)). Geometries and reaction energies were predicted for carbonate formation (chemisorption) and Lewis acid-base addition of CO (physisorption) to these (UO) clusters. Chemisorption of multiple CO moieties was also modeled for dimer and trimer clusters.