High pressure solid phases of benzene. I. Raman and x-ray studies of C6H6 at 294 K up to 25 GPa

Abstract

Crystalline benzene has been investigated at room temperature as a function of pressure up to 25 GPa in diamond anvil cells by Raman scattering and powder x-ray diffraction techniques. The concomitant spectroscopic and crystallographic results show the existence of numerous pressure-induced phases. Changes in the profiles of the Raman spectra and in the x-ray diffraction patterns, as well as changes in the variations of the Raman frequencies and the cell parameters with pressure indicate two first-order phase transitions at 1.4±0.1 and 4±1 GPa and a second-order one at 11±1 GPa. At 24 GPa the x-ray diffraction pattern seems to indicate the existence of a new phase. Two monoclinic structures are proposed for the phases above 1.5 GPa, in addition to the already known one. From these data, molar volume has been determined as a function of pressure and the Grüneisen parameters have been inferred in the different phases. Their pressure dependences are analyzed in the light of theoretical predictions. Arguments are given for a phase transformation at normal pressure and below 140 K or at room temperature below 1 GPa. A schematic P–T phase diagram is suggested and a controversy on the nature of the triple points located on the melting curve is clarified.