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Electronic structure of ferricenium ion from absorption, MCD, and ESR studies

The absorption and MCD spectra of the ferricenium ion have been measured at 290 and 9 °K. The data have been used, together with 20 °K ESR spectra to obtain quantitative information about the ground state of this molecule. The ground state emerges as a E‴(2Eg) state into which is mixed the E″(2Eg) state via a low symmetry perturbation. Evaluation of this from ESR and MCD data yield the values δ = 1043 cm−1 at 20 °K and δ = 263 cm−1 at 290 °K. The MCD strongly confirms the assignment of the electronic absorption band at 16 200 cm−1 as 2E2g → 2E1u.