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In situ high-pressure Raman spectra were collected on four pyroxenes, with composition CaCoSi2O6, CaMgSi2O6, CaCoGe2O6 and CaMgGe2O6, up to P = 7.6 and 8.3 GPa for silicates and germanates, respectively. The peak wavenumbers υi increase almost linearly with pressure; the slope dυi/d P is more pronounced for the modes at higher wavenumbers, and higher in germanates than in silicates. No phase transition or change in the compressional behaviour was observed within the investigated P-range. The strong dependence of the peak position with pressure of the high energy stretching modes is due to the high sensitivity of the vibrational frequencies probed by Raman spectroscopy to subtle changes in the tetrahedral deformation, which are overlooked by single-crystal X-ray diffraction. Copyright © 2017 John Wiley & Sons, Ltd. [ABSTRACT FROM AUTHOR]

The Raman spectra of Ge-clinopyroxenes CaM2+Ge2O6 (M2+ = Mg, Mn, Fe, Co, Ni, Zn), general formula M2M1T2O6, are reported for the first time. Their spectral features are discussed in comparison with corresponding Si-pyroxenes. The vibrational wavenumbers of germanates may be roughly obtained by a scale factor of about ~0.8 by those of the corresponding silicates, due to the Ge-Si mass difference. The main peaks in the germanate Raman spectra at ~850 and ~540 cm−1 may be related to Ge-O tetrahedral stretching and chain bending, respectively; minor peaks between 200 and 400 cm−1 are ascribed to bending and stretching of the non-tetrahedral cations. Within Ge-pyroxenes, possible correlations between crystallographic parameters and the vibrational wavenumbers are investigated. The main stretching mode at ~850 cm−1 shows wavenumber changes with M2+ substitutions, but no simple correlation can be found with M2+ cation mass or size. On the other hand, the chain bending wavenumber linearly decreases with increasing ionic radius of the M2+ cation: the expansion of the M1 polyhedron reduces the chain kinking angle and the Ge-Ge distances correspondingly increase. Copyright © 2015 John Wiley & Sons, Ltd. [ABSTRACT FROM AUTHOR]