Atomic Gold and Palladium Anion-Catalysis of Water to Peroxide: Fundamental Mechanism

We have performed dispersion-corrected density-functional transition state calculations on atomic Au- and Pd- catalysis of water conversion to peroxide. The Au- ion is found to be an excellent catalyst; however, atomic Pd- has a higher catalytic effect on the formation of peroxide. The Au^{-}(H2O)2 and Pd^{-}(H2O)2 anion molecular complexes formation in the transition state is identified as the fundamental mechanism for breaking the hydrogen bonding strength during the water catalysis. Our theoretical results provide crucial insight into the mechanism of the atomic Au- and Pd- catalysis in good agreement with recent experimental observations.