DFT and Proton Transfer Reactions: A Benchmark Study on Structure and Kinetics

Abstract

A significant number of different exchange correlation functionals, ranging from generalized gradient approximations to double hybrids, has been tested on a difficult playground represented by proton transfer reactions. In order to have a complete picture of their performances, both energetics and structural features have been compared and the obtained ranking compared with those issued from the standard test for kinetics (i.e., the DBH24/08 set). Among all of the functionals, the ωB97X, BMK, B1LYP, and PBE0-DH approaches are those providing a good error balance on all four trials. Beyond these figures, the obtained results allow for some general considerations, such as those on the role of Hartree–Fock exchange in reaction barriers or the relation between structure and energetics