The nature of stability and adsorption interactions of binary Au-Li clusters with bridge adsorption structures.

Earlier findings have confirmed that CO molecules have propensities to adsorb on low-coordinated gold atoms (top sites) of Au-based clusters, which can be treated by the Blyholder model wherein the σ donation and π-back donation take place. Here, the structural features and stability of (AuLi) n ( n = 1-9) clusters were first analyzed using the GA-DFT method. The new adsorption modes, vibration frequencies and electronic interactions for Au-Li clusters with CO were investigated in detail. More excitingly, we found that CO prefers to adsorb on the bridge sites of the Au-Li clusters rather than on the top sites, which are much lower in energies than the top adsorptions, and the C-O stretching frequencies are also red-shifted. AIMD simulations show that the adsorption structures still have good thermal stability at 500 K. The density of states reveals that the electronic structures of Au-Li clusters have excellent stability for the bridge adsorptions of CO molecules. The ETS-NOCV analysis and NPA charges show that the direction of charge flow is from Au-Li clusters → CO. Our study provides an idea to elucidate the new adsorption mechanism on Au-Li clusters and the connection between the geometries and reaction properties.