Raman Spectroscopy of High-Pressure−High-Temperature Polymorph of Hexahydro-1,3,5-trinitro-1,3,5-triazine (ε-RDX)

• Published in: The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Molecules, spectroscopy, kinetics, environment, & general theory, 2010-07, Vol.114 (26), p.7038-7047
• Main Authors: Dreger, Zbigniew A, Gupta, Yogendra M
• Format: Article
• Language: English
• Subjects: A: Kinetics, Spectroscopy
• ISSN: 1089-5639; 1520-5215
• DOI: 10.1021/jp102668d

Raman spectroscopy was used to determine the vibrational structure and the stability of the high-pressure−high-temperature (HP−HT) polymorph of RDX after it had been quenched to room temperature. Although this polymorph has limited chemical stability under high pressure and temperature, we show that it is chemically and structurally stable from 0.6 GPa to at least 20 GPa at room temperature. Below 0.6 GPa, it readily converts to the α-polymorph. Pressure dependence of the vibrational structure of the HP−HT polymorph was measured and compared with the vibrational structures of other known RDX polymorphs: α, β, and γ. In contrast with previous suggestions, our data indicate that the HP−HT polymorph can have a different structure than the β-polymorph. This finding supports the recent suggestion that the HP−HT polymorph should be given a separate designation, ε-RDX. Furthermore, symmetry correlation analyses of Raman spectra indicate that the HP−HT polymorph (ε-RDX) may assume the space group isomorphous with the C 2v [C 1(4)] point group and with molecules adopting the pseudo-AAA conformation.