Abstract
We have investigated the possibility of a link between the impact sensitivities of energetic compounds and the space available to their molecules in their crystal lattices. As a measure of this space, we use ΔV=Veff−V(0.002), where Veff is the effective molecular volume obtained from the crystal density and V(0.002) is that enclosed by the 0.002 au contour of the molecule’s gas phase electronic density, determined computationally. When experimental impact sensitivity was plotted against ΔV for a series of 20 compounds, the nitramines formed a separate group showing little dependence upon ΔV. Their impact sensitivities correlate well with an anomalous imbalance in the electrostatic potentials on their molecular surfaces, which is characteristic of energetic compounds in general. The imbalance is symptomatic of the weakness of the N–NO2 bonds, caused by depletion of electronic charge. The impact sensitivities of non-nitramines, on the other hand, depend much more strongly upon ΔV, and can be quite effectively related to it if an electrostatically-based correction term is included.
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MP and PV acknowledge the support of this work by the Ministry of Education, Youth and Sports of the Czech Republic as a part of its research projects Nos. MSM0021620835 (MP) and MSM0021627501 (PV), respectively. PP, JSM and MCC appreciate the support of the Defense Threat Reduction Agency, Contract No. HDTRA1-07-1-0002, Project Officer Dr. William Wilson.
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Pospíšil, M., Vávra, P., Concha, M.C. et al. A possible crystal volume factor in the impact sensitivities of some energetic compounds. J Mol Model 16, 895–901 (2010). https://doi.org/10.1007/s00894-009-0587-x
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DOI: https://doi.org/10.1007/s00894-009-0587-x