The performance of density functional approximations for the structures and relative energies of minimum energy crossing points

Abstract

The structural parameters and relative energies of the minimum-energy crossing points (MECPs) of eight small molecules are calculated using five different representative density functional theory approximations as well as MP2, MP4, and CCSD(T) as a reference. Compared to high-level wavefunction methods, the main structural features of the MECPs of the systems included in this Letter are reproduced reasonably well by density functional approximations, in agreement with previous works. Our results show that when high-level wavefunction methods are computationally prohibitive, density functional approximations offer a good alternative for locating and characterizing the MECP in spin-forbidden chemical reactions.