Relativistic scattered wave calculations of hexachloro- and hexabromoiridate (IV)

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Abstract
Dirac scattered-wave (DSW) calculations are reported for the ground and several excited states [IrCl6]2− and [IrBr6]2−, and comparisons are made to electron spin resonance, optical absorption, and magnetic circular dichorism spectra. Metal and ligand-centered contributions to the Zeeman and hyperfine tensors differ from those estimated from ligand field theory, although both calculations are in qualitative agreement with experiment. The predicted symmetries and spin-orbit splittings of ligand-to-metal charge transfer transitions are approximately correct, but the estimated transitions energies are too low by 0.2–0.7 eV. The implications of this behavior for future relativistic Xα calculations are discussed, with an emphasis on various approximate methods of including spin-polarization effects in relativistic calculations.