On the Stability of Cu(5) Catalysts in Air Using Multireference Perturbation Theory

[Image: see text] An ab initio study of the interaction of O(2), the most abundant radical and oxidant species in the atmosphere, with a Cu(5) cluster, a new generation atomic metal catalyst, is presented. The open-shell nature of the reactant species is properly accounted for by using the multireference perturbation theory, allowing the experimentally confirmed resistivity of Cu(5) clusters toward oxidation to be investigated. Approximate reaction pathways for the transition from physisorption to chemisorption are calculated for the interaction of O(2) with quasi-iso-energetic trapezoidal planar and trigonal bipyramidal structures. Within the multireference approach, the transition barrier for O(2) activation can be interpreted as an avoided crossing between adiabatic states (neutral and ionic), which provides new insights into the charge-transfer process and gives better estimates for this hard to localize and therefore often neglected first intermediate state. For Cu(5) arranged in a bipyramidal structure, the O–O bond cleavage is confirmed as the rate-determining step. However, for planar Cu(5), the high energy barrier for O(2) activation, related to a very pronounced avoided crossing when going from physisorption to chemisorption, determines the reactivity in this case.