High Pressure Raman Spectroscopy of Single Crystals of Hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX)
- 23 March 2007
- journal article
- Published by American Chemical Society (ACS) in The Journal of Physical Chemistry B
- Vol. 111 (15), 3893-3903
- https://doi.org/10.1021/jp0681092
Abstract
To gain insight into the high-pressure polymorphism of RDX, an energetic crystal, Raman spectroscopy results were obtained for hydrostatic (up to 15 GPa) and non-hydrostatic (up to 22 GPa) compressions. Several distinct changes in the spectra were found at 4.0 ± 0.3 GPa, confirming the α−γ phase transition previously observed in polycrystalline samples. Detailed analyses of pressure-induced changes in the internal and external (lattice) modes revealed several features above 4 GPa: (i) splitting of both the A‘ and A‘ ‘ internal modes, (ii) a significant increase in the pressure dependence of the Raman shift for NO2 modes, and (iii) no apparent change in the number of external modes. It is proposed that the α−γ phase transition leads to a rearrangement between the RDX molecules, which in turn significantly changes the intermolecular interaction experienced by the N−O bonds. Symmetry correlation analyses indicate that the γ-polymorph may assume one of the three orthorhombic structures: D2h, C2v, or D2. On the basis of the available X-ray data, the D2h factor group is favored over the other structures, and it is proposed that γ-phase RDX has a space group isomorphous with a point group D2h with eight molecules occupying the C1 symmetry sites, similar to the α-phase. It is believed that the factor group splitting can account for the observed increase in the number of modes in the γ-phase. Spatial mapping of Raman modes in a non-hydrostatically compressed crystal up to 22 GPa revealed a large difference in mode position indicating a pressure gradient across the crystal. No apparent irreversible changes in the Raman spectra were observed under non-hydrostatic compression.Keywords
This publication has 24 references indexed in Scilit:
- Chemical Reactions and Other Behaviors of High Energetic Materials under Static Ultrahigh PressuresMaterials Science Forum, 2004
- Vibrational Spectroscopy Study of β and α RDX DepositsThe Journal of Physical Chemistry B, 2004
- Raman Spectroscopy of Pentaerythritol Single Crystals under High PressuresThe Journal of Physical Chemistry B, 2004
- High-Pressure Effects on Fluorescence of Anthracene CrystalsThe Journal of Physical Chemistry B, 2003
- Reinvestigation of the Gas-Phase Structure of RDX Using Density Functional Theory Predictions of Electron-Scattering IntensitiesThe Journal of Physical Chemistry A, 2002
- Raman effects under pressure in chloroadamantane plastic crystalJournal of Physics: Condensed Matter, 2002
- Moissanite: A Window for High-Pressure ExperimentsScience, 2000
- Ab Initio and Nonlocal Density Functional Study of 1,3,5-Trinitro-s-triazine (RDX) ConformersThe Journal of Physical Chemistry A, 1997
- Influence of pressure and temperature on phonons in molecular chalcogenides: Crystalline andPhysical Review B, 1978
- Pressure-Raman effects and vibrational scaling laws in molecular crystals: andPhysical Review B, 1974