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A CASPT2 study of the electronic spectrum of hexacyanoosmate(III)
Willem Van den Heuvel1, Marc F A Hendrickx, Arnout Ceulemans
1Department of Chemistry, Katholieke Universiteit Leuven, Celestijnenlaan 200F, B-3001 Leuven, Belgium. willem.vandenheuvel@chem.kuleuven.be
Abstract:
CASPT2 calculations reveal that the ligand field splitting parameter Delta(o) of [Os(CN)6]3- is much higher than previously proposed values of +/-38,000 cm(-1). In line with the expected increase down a transition-metal group, Delta(o) is found to be +/-55,000 cm(-1), excluding the possible appearance of ligand field transitions in the UV-vis spectrum. Instead, the calculations confirm that the observed spectrum arises from the three lowest symmetry-allowed ligand-to-metal charge-transfer (LMCT) excitations. Spin-orbit coupling in the ground state is found to be about 4350 cm(-1), leading to a spin-orbit coupling constant zeta of +/-2900 cm(-1). Spin-orbit coupling in the 2T(1u) LMCT states is found not to be negligible, contrary to previous belief.
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