Density functional theory (DFT) was used to study reactions involving
small molecules. Relative energies of isomers and transition structure
s of diazene, formaldehyde, and methylenimine were determined using va
rious DFT functionals and results were compared with MP2 and MP4 calcu
lations. DFT reaction barriers were found to be consistently lower. Fo
r some reactions, such as OH + H-2 --> H2O + H, gradient-corrected fun
ctionals predict very low or nonexistent barriers. The hybrid Hartree-
Fock-DFT adiabatic connection method (ACM) often provides much better
results in such cases. The performance of several density functionals,
including ACM, was tested in calculations on over 100 atomization, hy
drogenation, bond dissociation, and isodesmic reactions. The ACM funct
ional provides consistently better geometries and reaction energetics
than does any other functional studied. In cases where both HF and gra
dient-corrected DFT methods underestimate bond distances, the ACM geom
etries may be inferior to those predicted by gradient-corrected DFT me
thods. (C) 1995 John Wiley & Sons, Inc.