Electric field gradients of transition metal complexes from density functional theory: assessment of functionals, geometries and basis sets

Abstract

Electric field gradients (EFGs) were computed for the first-row transition metal nuclei in Cr(C₆H₆)(CO)₃, MnO₃F, Mn(CO)₅H, MnCp(CO)₃, Co(CO)₄H, Co(CO)₃(NO) and VCp(CO)₄, for which experimental gas-phase data (in form of nuclear quadrupole coupling constants) are available from microwave spectroscopy. A variety of exchange–correlation functionals were assessed, among which range-separated hybrids (such as CAM-B3LYP or LC-ωPBE) perform best, followed by global hybrids (such as B3LYP and PBE0) and gradient-corrected functionals (such as BP86). While large basis sets are required on the metal atom for converged EFGs, smaller basis sets can be employed on the ligands. In most cases, EFGs show little sensitivity toward the geometrical parameters.