Ab Initio Investigation of Spectroscopic Parameters for CrX63–: The Unexpected Role of Bond Length Variation – Size Really Matters

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AbstractLigand field states were calculated in the CrX63– series with X = F, Cl, Br, and I from first principles, and the ligand field parameter, Δ, was deduced. The decrease in Δ follows the spectrochemical series; π effects are usually invoked to justify this trend. It is shown that while the covalence increases, the π effect decreases and that the key role in the decrease in Δ is played by the increase in bond length in the halide series.