Evaluations of the accuracies of DMol3 density functionals for calculations of experimental binding enthalpies of N2, CO, H2, C2H2 at catalytic metal sites

The density functionals that can be used with numerical basis sets in the density functional methodology of the programme DMol3 are evaluated by comparison with experimental data. The objective is to identify and validate the most accurate and computationally efficient density functional to be used in DMol3 simulations that use large molecular models (many hundreds of atoms) of the reaction steps involved in the chemical mechanisms of metalloenzymes and synthetic metallocatalysts. The experimental systems focus on enthalpy data for reactions analogous to those involved in the chemical mechanism of nitrogenase, including coordination of N2, CO, H2 and C2H4 and hydrogen bonding. Some geometric and vibrational frequency data are included in the 19 test systems. The conclusion is that the gradient-corrected functionals PBE, PW91 and BP provide acceptably accurate results, with the best functional being PBE, which yields reaction energies within or very close the experimental error range. These functionals are also the most computationally efficient.