An evaluation of the density functional approach in the zero order regularapproximation for relativistic effects: Magnetic interactions in small metal compounds

The performance of the density functional approach in the relativistic zero order regular approximation for the evaluation of electron spin resonance (ESR) parameters in small metal compounds has been evaluated critically by comparison with experimental data and available theoretical results for 22 linear molecules, characterized by a (2)Sigma electronic ground state. For most of the molecules studied the calculated magnetic parameters are in goo d (A tensors) or reasonable (g tensors) agreement with experiment. Effects of spin-orbit coupling and spin polarization on the calculated hyperfine in teraction are investigated. These two effects can only be evaluated separat ely, since the present method does not allow us to take spin-polarization e ffects into account in spin-orbit coupled density functional calculations. However, while spin-polarization effects are important for all the molecule s investigated, spin-orbit effects are non-negligible only for the molecule s containing heavier metal atoms. The ESR parameters, evaluated using diffe rent "standard" exchange-correlation potentials, have only shown little dep endence on the specific functional. Direct relativistic contributions to th e hyperfine parameters are often large, especially for the heavier metals, but also "secondary" contributions to the ligand hyperfine parameters can b e large if the ligand is bound to a heavy element. (C) 2001 American Instit ute of Physics.