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 alpha-gamma 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 alpha-gamma 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 gamma-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 gamma-phase RDX has a space group isomorphous with a point group D2h with eight molecules occupying the C1 symmetry sites, similar to the alpha-phase. It is believed that the factor group splitting can account for the observed increase in the number of modes in the gamma-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.

The decomposition mechanism in shocked pentaerythritol tetranitrate (PETN) was examined using timeresolved emission spectroscopy. PETN single crystals were subjected to stepwise loading along [100] and [110] to peak stresses between 2 and 13 GPa. Due to concurrent changes in the optical transmission of PETN, emission spectra were analyzed using the absorption data acquired separately under the same loading conditions. Analyses of the corrected emission data revealed two bands in the spectra at ∼3.0 and ∼2.4 eV. Both bands were observed in every experiment regardless of stress or crystal orientation. However, their relative and absolute intensities, and temporal behavior revealed stress and orientation dependence. The emission was identified as chemiluminescence from the nitronium ion, NO 2 + , on the basis of its electronic structure and properties. NO 2 + electronic structure was analyzed using ab initio calculations, which showed transition energies matching those of the emitting intermediate observed experimentally. Several chemical pathways compatible with the formation of NO 2 + are considered and evaluated. Finally, a four-step chemical initiation mechanism in shocked crystalline PETN is proposed and discussed in detail.

Raman spectroscopy and optical imaging were used to determine the phase boundaries between various hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) polymorphs. Experiments were performed on single crystals at pressures up to 8.0 GPa and temperatures ranging from room temperature to 550 K. Several distinct pressure regions were found in the RDX response at elevated temperatures: (i) melting of alpha-RDX followed by decomposition, below 2.0 GPa, (ii) decomposition of alpha-RDX between 2.0 and 2.8 GPa, (iii) irreversible transformation of alpha- and gamma-RDX to epsilon-RDX between 2.8 and 6.0 GPa, and (iv) decomposition of gamma-RDX above 6.0 GPa. A triple point between the alpha-, gamma-, and epsilon-RDX was found at 3.7 GPa and 466 K. The alpha-gamma phase transition was confirmed to occur at the same pressure, approximately 3.7 GPa, regardless of temperature, in the range of 295-460 K. Furthermore, it was determined that epsilon-RDX (i) has limited chemical stability under the pressure and temperature conditions where it is produced and (ii) decomposes according to the autocatalytic rate law. The findings reported here have provided new information about the response of RDX crystals at high pressures and temperatures.

The effects of high pressures (up to 40 kbar) on the dihydrogen-bonded BH3NH3 molecular crystal were investigated using Raman spectroscopy in diamond and moissanite anvil cells. The stretching mode frequencies of the NH3 proton donor groups exhibited moderate red shifts with increasing pressures, as found in many conventional hydrogen-bonded systems of weak to medium strength. The stretching modes corresponding to the BH3 proton acceptor group, on the other hand, showed large blue shifts with increasing pressure, which, however, are not related to the changes in the N−H···H−B interactions. The BH3NH3 crystals undergo a pressure-induced disorder−order phase transition around 8 kbar, which is facilitated by the presence of dihydrogen bonds.

The real-time, molecular-level response of oriented single crystals of hexahydro-1,3,5-trinitro-s-triazine (RDX) to shock compression was examined using Raman spectroscopy. Single crystals of [111], [210], or [100] orientation were shocked under stepwise loading to peak stresses from 3.0 to 5.5 GPa. Two types of measurements were performed: (i) high-resolution Raman spectroscopy to probe the material at peak stress and (ii) time-resolved Raman spectroscopy to monitor the evolution of molecular changes as the shock wave reverberated through the material. The frequency shift of the CH stretching modes under shock loading appeared to be similar for all three crystal orientations below 3.5 GPa. Significant spectral changes were observed in crystals shocked above 4.5 GPa. These changes were similar to those observed in static pressure measurements, indicating the occurrence of the alpha-gamma phase transition in shocked RDX crystals. No apparent orientation dependence in the molecular response of RDX to shock compression up to 5.5 GPa was observed. The phase transition had an incubation time of approximately 100 ns when RDX was shocked to 5.5 GPa peak stress. The observation of the alpha-gamma phase transition under shock wave loading is briefly discussed in connection with the onset of chemical decomposition in shocked RDX.

Time-resolved optical spectroscopy was used to examine chemical decomposition of RDX crystals shocked along the [111] orientation to peak stresses between 7 and 20 GPa. Shock-induced emission, produced by decomposition intermediates, was observed over a broad spectral range from 350 to 850 nm. A threshold in the emission response of RDX was found at about 10 GPa peak stress. Below this threshold, the emission spectrum remained unchanged during shock compression. Above 10 GPa, the emission spectrum changed with a long wavelength component dominating the spectrum. The long wavelength emission is attributed to the formation of NO2 radicals. Above the 10 GPa threshold, the spectrally integrated intensity increased significantly, suggesting the acceleration of chemical decomposition. This acceleration is attributed to bimolecular reactions between unreacted RDX and free radicals. These results provide a significant experimental foundation for further development of a decomposition mechanism for shocked RDX (following paper in this issue).

Raman spectroscopy was used to examine the vibrational and polymorphic behavior of 1,1-diamino-2,2-dinitroethene (FOX-7) to elucidate its structural and chemical stability under high pressure. Measurements were performed on single crystals compressed in a diamond anvil cell, and data were obtained over the entire frequency range of FOX-7 Raman activity. Several new features were observed with increase of pressure: (i) new vibrational peaks and discontinuity in the shifts of the peaks at 2 and 4.5 GPa, (ii) apparent coupling or mixing of several modes, and (iii) changes in the NH2 stretching spectral shape and modes shift. The spectral changes at 2 GPa, in contrast to previous reports, involved only a few peaks and likely resulted from a small molecular transformation. In contrast, changes at 4.5 GPa involved most of the modes, and the pressure for the onset and completion of the changes depended on the pressure medium. A large pressure hysteresis regarding the changes at 4.5 GPa implies a reconstructive transformation. We suggest that this transformation reflects a change in the balance between interlayer (van der Waals) and in-layer (H-bonding) interactions. Despite these transformations, further compression to 40 GPa and subsequent release of pressure did not cause any irreversible changes. This finding implies that FOX-7 has remarkable chemical stability under high pressures. The observed coupling between the various modes with increasing pressure was analyzed within the Fermi resonance model. The potential implication of the coupling of modes for shock insensitivity of FOX-7 is briefly discussed.

Raman measurements and density functional theory (DFT) calculations were carried out to evaluate the propensity of pentaerythritol tetranitrate (PETN) to conformational changes. In the crystalline phase under ambient conditions, the PETN molecule has S 4 symmetry. Two instances of symmetry change were found and presented in this work. One involved compressing the PETN crystal statically to ≥5 GPa in a diamond anvil cell. The other was observed upon dissolving PETN in a polar solvent (acetone-d 6). DFT calculations indicate that changes in conformation/symmetry can be observed readily through changes in the vibrational spectrum. Several representative stable PETN conformations of various symmetries were found and examined. The calculated Raman spectra provide support for the conclusion that the S 4 symmetry, at ambient conditions, changes to C 2 under static high-pressure loading and to C 2 or C 1 in solution.