Raman spectroscopic study of hydroxyl-clinohumite at various pressures and temperatures

Abstract

Variations of Raman spectra of hydroxyl-clinohumite were studied up to ∼370 kbar at room temperature, and in the range 81–873 K at atmospheric pressure. With the exception of the symmetric OH-stretch bands, the Raman frequencies of all bands were observed to increase monotonically with increasing pressure, and decrease with increasing temperature. This behavior is in line with those observed for other humite members (norbergite and chondrodite) so far studied. The symmetric OH-stretching band shows a mode softening with increasing pressure, and splits into two bands at either high pressure or low temperature. In the quasihydrostatic experiment, the compression and decompression paths of one of the asymmetric OH-stretch bands form a hysteresis loop, but the same behavior was not observed in the nonhydrostatic experiment. These results indicate that the two kinds of OH groups in hydroxyl-clinohumite have nonequivalent movement paths on compression, and with one OH group experiencing a release of spatial hindrance during compression. This behavior appears to be modified by shear stress. The same complication of the OH groups was not observed in the temperature variation study. The pressure and temperature variations of the Raman frequencies for the various vibrations involving the SiO4 tetrahedra and MgO6 octahedra below ∼1000 cm−1 for clinohumite behave similarly to other hydrous magnesium silicates. On the basis of the relationship between isothermal bulk modulus and Raman data, it is suggested that the linear pressure dependences of vibrational frequencies of various Raman bands reported in the literature are inadequate.