Authors: Zanchet, Alexandre; Lopez-Caballero, Patricia; Mitrushchenkov, Alexander O.; Buceta, David; Arturo Lopez-Quintela, Manuel; Hauser, Andreas W.;  de Lara-Castells, Maria Pilar

Contribution: Article


Publication date: 2019/11/07

DOI: 10.1021/acs.jpcc.9b08378

Abstract: 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.