Databases for Transition Element Bonding: Metal-Metal Bond Energies and Bond Lengths and Their Use to Test Hybrid, Hybrid Meta, and Meta Density Functionals and Generalized Gradient Approximations

J Phys Chem A. 2005 May 19;109(19):4388-403. doi: 10.1021/jp0504468.


We propose a data set of bond lengths for 8 selected transition metal dimers (Ag(2), Cr(2), Cu(2), CuAg, Mo(2), Ni(2), V(2), and Zr(2)) and another data set containing their atomization energies and the atomization energy of ZrV, and we use these for testing density functional theory. The molecules chosen for the test sets were selected on the basis of the expected reliability of the data and their ability to constitute a diverse and representative set of transition element bond types while the data sets are kept small enough to allow for efficient testing of a large number of computational methods against a very reliable subset of experimental data. In this paper we test 42 different functionals: 2 local spin density approximation (LSDA) functionals, 12 generalized gradient approximation (GGA) methods, 13 hybrid GGAs, 7 meta GGA methods, and 8 hybrid meta GGAs. We find that GGA density functionals are more accurate for the atomization energies of pure transition metal systems than are their meta, hybrid, or hybrid meta analogues. We find that the errors for atomization energies and bond lengths are not as large if we limit ourselves to dimers with small amounts of multireference character. We also demonstrate the effects of increasing the fraction of Hartree-Fock exchange in multireference systems by computing the potential energy curve for Cr(2) and Mo(2) with several functionals. We also find that BLYP is the most accurate functional for bond energies and is reasonably accurate for bond lengths. The methods that work well for transition metal bonds are found to be quite different from those that work well for organic and other main group chemistry.