%0 Journal Article %A García-Cruz, Raúl %A Poulain, Enrique %A Hernández-Pérez, Isaías %A Reyes-Nava, Juan A. %A González-Torres, Julio C. %A Rubio-Ponce, A. %A Olvera-Neria, Oscar %D 2017 %T Effect of Spin Multiplicity in O2 Adsorption and Dissociation on Small Bimetallic AuAg Clusters %U https://acs.figshare.com/articles/journal_contribution/Effect_of_Spin_Multiplicity_in_O_sub_2_sub_Adsorption_and_Dissociation_on_Small_Bimetallic_AuAg_Clusters/5281879 %R 10.1021/acs.jpca.7b01968.s001 %2 https://ndownloader.figshare.com/files/9045448 %K bimetallic clusters %K O 2 adsorption energy %K O 2 Adsorption %K Ag atoms %K O 2 activation %K O 2 adsorption %K O 2 %K DFT %K n Ag m %K n Ag m clusters %K Small Bimetallic AuAg Clusters %K ZORA %K bond %X To dispose of atomic oxygen, it is necessary the O2 activation; however, an energy barrier must be overcome to break the O–O bond. This work presents theoretical calculations of the O2 adsorption and dissociation on small pure Aun and Agm and bimetallic AunAgm (n + m ≤ 6) clusters using the density functional theory (DFT) and the zeroth-order regular approximation (ZORA) to explicitly include scalar relativistic effects. The most stable AunAgm clusters contain a higher concentration of Au with Ag atoms located in the center of the cluster. The O2 adsorption energy on pure and bimetallic clusters and the ensuing geometries depend on the spin multiplicity of the system. For a doublet multiplicity, O2 is adsorbed in a bridge configuration, whereas for a triplet only one O–metal bond is formed. The charge transfer from metal toward O2 occupies the σ*O–O antibonding natural bond orbital, which weakens the oxygen bond. The Au3 (2A) cluster presents the lowest activation energy to dissociate O2, whereas the opposite applies to the AuAg (3A) system. In the O2 activation, bimetallic clusters are not as active as pure Aun clusters due to the charge donated by Ag atoms being shared between O2 and Au atoms. %I ACS Publications