Incorporation of Cr 3+ in dickite: a spectroscopic study

We have investigated a well-ordered sample of natural Cr-bearing dickite from Nowa Ruda (Lower Silesia, Poland) using electron paramagnetic resonance (EPR) at X- and Q-band frequencies (9.42 and 33.97 GHz, respectively) and optical diffuse reflectance spectroscopy. The observation of the spin-forbidden transitions at 15500 and 14690 cm−1 allows us to unambiguously identify the major contribution of octahedrally coordinated Cr3+ ions in the optical spectrum. The X- and Q-band EPR spectra show two superposed Cr3+ signals. The corresponding fine-structure parameters were determined at room temperature and 145 K. These results suggest the substitution of Cr3+ for Al3+ in equal proportions in the two unequivalent octahedral sites of the dickite structure. In kaolin group minerals, the distortion around Cr3+ ions (λ≈ 0.2–0.4) in Al sites is significantly less rhombic than that observed around Fe3+ ions (λ≈ 0.6–0.8).