Abstract
The surfaces of solution-grown β-HMX (β-octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine) crystals were studied using vibrational sum-frequency generation spectroscopy (SFG). In earlier work (Kim, H.; Lagutchev, A.; Dlott, D. D. Propellants, Explosives, Pyrotechnics 2005, 31, 116), such SFG spectra evidenced considerable variability as the ∼200-μm diameter laser beam was translated over crystal surfaces. We have now found this variability results from ubiquitous small deposits of δ-HMX on the surface of β-HMX single crystals. SFG is a selective probe of molecules in noncentrosymmetric environments. Since β-HMX is centrosymmetric, only the surface is SFG-active; however, δ-HMX is noncentrosymmetric, so a tiny δ-HMX deposit on a β-HMX surface could dominate the SFG spectrum. We have found that rapid evaporation from tiny droplets of HMX solution produces only δ-HMX, presumably because the polar boat conformation of δ-HMX is stabilized in solution. We believe the δ-HMX deposits are created by the rapid dryin...
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