Can DFT and ab initio methods describe all aspects of the potential energy surface of cycloreversion reactions

摘要: AbstractWe introduce a representative benchmark database of 20 cycloreversion reaction energies obtained by means the high-level W1 thermochemical protocol. We use these values to assess performance variety contemporary DFT, double-hybrid DFT (DHDFT), standard ab initio, and compound thermochemistry methods. show that this set provides an extremely challenging test for nearly all considered DHDFT For example, about 80% functionals result in root-mean-square deviations (RMSDs) above 10 kJ mol−1. The best procedures are ωB97X DSD-PBEP86-D3, with RMSDs 4.7 7.9 kJ mol−1, respectively. Coupled fact barrier heights reactions also pose significant challenge many methods, work shows only handful can quantitatively describe aspects potential energy surface important class reactions. In addition, tha...