Reaction barrier heights from an exact-exchange-based density-functional correlation model

摘要

A recent exact-exchange-based density-functional model of nondynamical and dynamical correlation [A.D.Becke,J.Chem.Phys.122,064101 (2005)] is tested on 70 barrier heights for a variety of reaction types:hydrogen transfer reactions,heavy-atom transfer,reactions,nucleophilic substitutions,association reactions,and unimolecular rearrangements,including both even- and odd-electron systems.The mean absolute error with respect to accurate reference,data is 1.4 kcal/mol.This is achieved without any refitting of the parameters of the model to the barrier height data.