Single crystal absorption spectra of synthetic Ti, Fe-substituted pyropes

Abstract

Synthetic pyrope crystals up to 0.5 mm in diameter, substituted by titanium or by titanium plus iron, were grown under defined conditions of P, T, $$f_{O_2 }$$ in the presence of water using a piston-cylinder device. The crystals were characterized by X-ray and microprobe techniques. Their single-crystal optical absorption spectra were measured by means of a microscope-spectrometer. Two absorption bands at 16100 and 22300 cm{cm-1} in the spectra of pale-blue Fe-free Ti-bearing pyropes, grown under reduced conditions, were identified as originating from spin-allowed transitions, derived from 2 T 2g → 2 E g of octahedral Ti3+ ions. The splitting value of the excited 2E g state, 6200 cm-1, and the crystal field parameter of Ti3+ in pyrope Δ 0 = 19 200 cm-1 are both in agreement with literature data. In spectra of brown Fe, Ti-bearing garnets, a broad band at 23000 cm-1 was interpreted as a Fe2+[8] → Ti4+[6] charge-transfer band. The spectral position and width of this band agree with those observed for a FeTi charge transfer band in natural garnets. Fe, Ti-containing garnets synthesized at relatively high oxygen fugacity (10-11,0 atm), which permits a fraction of Fe3+ to enter the garnet, show an additional Fe2+[8] → Fe3+[6] charge transfer band at 19800 cm-1.