An investigation of density functionals: The first-row transition metal dimer calculations

The performance of different density functional theory (DFT) methods was in vestigated in the calculations of the bond length and the binding energy of the first-low transition metal dimers. The 4s-3d interconfigurational ener gies and 4s and 3d ionization potentials were also calculated for the first -row transition metal atoms. In general, the hybrid DFT method, B3LYP, yiel ds the bond lengths that are too short compared to the experimental ones. I n contrast, the optimized bond lengths by nonhybrid DFT methods such as BOP or PW91 are in good agreement with the experiment. It was also found that nonhybrid DFT methods overestimate the binding energies, because they have a tendency to overstabilize the electron configurations that contain the at omic and molecular orbitals in a higher angular momentum open shell. The hy brid DFT method yields more accurate binding energies, but it estimates rat her poor energy gaps between states whose spin multiplicity is quite differ ent. (C) 2000 American Institute of Physics. [S0021-9606(00)31002-9].