Vibronic Spectra of Transition-Metal Complexes I. Polarized Emission and Absorption Spectra of NaMg[Cr(C2O4)3]·9H2O

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Abstract
Polarized emission and absorption spectra of NaMg[Cr(C2O4)3]·9H2O have been obtained at temperatures between 4.5° and 300°K in the frequency range 13 000–45 000 cm−1. Some doublet and all quartet states belonging to the electronic (3d)3 configuration have been located and several vibronic states identified. The intensities of the Laporte‐forbidden transitions have been analyzed in terms of electronic and vibronic contributions, and it is shown (i) that both static and dynamic effects are important, (ii) that several vibrational modes are effective, and further, (iii) that even very low‐frequency vibrations (phonons) are important. Fine structure has been resolved in the two no‐phonon lines corresponding to the electronic transition 4A2→2E, and is assigned to exchange interactions between separate Cr3+ ions.