Relativistic DFT calculation and their effect on the accuracy of results

Abstract

This study explores the significance of density functional theory (DFT) calculations with relativistic effects for two ethylenediaminetetraacetate (edta) type complexes: trans(O5)-[M(eddadp)]- (M = Rh3+, Co3+). Relativistic effects affect the electronic structure of a molecule and, thus, its chemical and spectroscopic properties. With the use of scalar relativistic corrections (SR-ZORA), as implemented in the ADF package, with the B3LYP functional, the TZP basis set and the COSMO solvation model, structural analyses show improved predictions for the geometries of both complexes. In the case of the Rh3+ complex, the differences in metal-ligand bond lengths with and without the relativistic effects were small. In the case of the Co3+ complex, the changes in metal-ligand bond lengths due to the relativistic effects were slightly more pronounced. Compared to experimental values, excitation energies are better when including relativistic corrections, especially for the Rh3+ complex. These results indicate the importance of relativistic DFT calculations for heavy element compounds.