PNNL

Abstract

A systematic assessment of theoretical methods applicable to the accurate characterization of catalytic cycles of homogeneous catalysts for H2 oxidation and evolution is reported. For these catalysts, H2 bond breaking or formation involve di-hydrogen, di-hydride, hydride-proton, and di-proton complexes. The key elementary steps have heterolytic character. In the context of Density Functional Theory (DFT) we investigated the use of functionals in the generalized gradient approximation (GGA) as well as hybrid functionals. We compared the results with wavefunction theories based on perturbation theory (MP2 and MP4) and on coupled-cluster expansions (CCSD and CCSD(T)). Our findings suggest that DFT results based on Perdew functionals are in semi-quantitative agreement with the CCSD(T) results, with deviations of a few kcal/mol only. On the other hand, the B3LYP functional is not even in qualitative agreement with CCSD[T]. Surprisingly the MP2 results are found to be extremely poor, a finding that we attribute to the limited treatment in MP2 theory of dynamic electron correlation effects in Ni(0) oxidation state. This material is based upon work supported as part of the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the US Department of Energy, Office of Science, Office of Basic Energy Sciences.