DFT Study of the Reaction Mechanism of N 2 O Decomposition on Au 3 +/0/− Clusters

In this paper, the reaction mechanism of Au 3 +/0/− clusters with N 2 O was studied by density functional theory (DFT) calculations. The analysis of the potential energy surfaces showed that the Au 3 neutral cluster exhibited highest catalytic activity on the decomposition of N 2 O, energy barrier is only 11.60 kcal/mol. The corresponding energy barriers for Au 3 − and Au 3 + are 28.51 and 58.79 kcal/mol, respectively. The effects of Au 3 +/0/− clusters assistance analyzed using the activation strain model indicated that the dissociation of the N−O bond depends on the interaction energy of Au 3 clusters and N 2 O. The electron transfer from the Au 3 +/0/− cluster to the N 2 O facilitates the dissociation of N−O bond. The analysis of frontier molecular orbitals (FMO) indicated that only the interaction of HOMO‐LUMO interactions is strongly enough and there is sufficient orbital overlap between the Au 3 +/0/− clusters and N 2 O, electron transfer can occur and activation of N 2 O can be achieved. The study of thermodynamic processes showed that there is evident correlation between the binding energy of the Au 3 O +/0/− cluster oxides and the barrier energy of the reaction. Therefore, the orbital interactions between Au 3 +/0/− and N 2 O and thermodynamic driving force have a great influence on the reaction. These results enrich our understanding of the catalytic dissociation of N 2 O by Au‐cluster‐based catalysts.