PNNL

Abstract

The research described in this product was performed in part in the Environmental Molecular Sciences Laboratory, a national scientific user facility sponsored by the Department of Energy's Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory. Saddle point properties of three symmetric and one asymmetric hydrogen transfer and the energy of reaction of the asymmetric reactions are investigated in the present work. These reactions were calculated by various density functionals, many of which were developed in recent years, by coupled cluster theory, and by multicoefficient correlation methods based on wave function theory. Instead of comparing calculated results to “semi-experimental” values, we compared them to very accurate theoretical values (e.g., to values obtained by the Weizmann-1 method). Coupled cluster theory and the multicoefficient correlation methods MC-QCISD/3 and MCQCISD-MPW are very accurate for these reactions with mean unsigned errors below 0.94 kcal/mol. Diagnostics for multireference character add additional reliability to these results. The newly developed hybrid density functional M06-2X shows very good performance for these reactions with a mean unsigned error of only 0.77 kcal/mol; the BHandHLYP, MPW1K, and BB1K density functionals, can also predict these reactions well with mean unsigned errors less than 1.42 kcal/mol.