Broadband terahertz time-domain spectroscopy (THz-TDS) has been used to measure the far-infrared (FIR) vibrational spectra of several commonly used pure explosives, including 2,4,6-trinitrotoluene (TNT), 1,3,5-trinitroperhydro-1,3,5-triazine (RDX), 1,3-dinitrato-2,2-bis(nitratomethyl)propane (PETN), and two types of plastic explosive, SEMTEX and SX2. A number of distinct absorption peaks, originating from FIR-active vibrational modes of these polycrystalline energetic materials, were observed in the frequency range 0.3–7.5 THz (10–250 cm<sup>−1</sup>). In addition, the temperature-dependent FIR vibrational spectra of PETN were measured between 4 K and 296 K with several well-resolved absorption peaks observed across this temperature range. We find that as the temperature is reduced, the observed absorption peaks resolve into narrower features and shift towards higher frequencies. The temperature dependence of the spectra is explained in terms of the anharmonicity of the vibrational potentials of crystalline compounds, and an empirical fit is given to describe the peak shift with temperature.

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