A possible crystal volume factor in the impact sensitivities of some energetic compounds.
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 Delta V=V(eff)-V(0.002), where V(eff) 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 Delta V for a series of 20 compounds, the nitramines formed a separate group showing little dependence upon Delta V. 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-NO(2) bonds, caused by depletion of electronic charge. The impact sensitivities of non-nitramines, on the other hand, depend much more strongly upon Delta V, and can be quite effectively related to it if an electrostatically-based correction term is included.
Pospísil
Miroslav
M
Faculty of Mathematics and Physics, Charles University, Ke Karlovu 3, CZ 12116, Prague 2, Czech Republic.
Vávra
Pavel
P
Concha
Monica C
MC
Murray
Jane S
JS
Politzer
Peter
P
D000814:Aniline Compounds / Q000737:chemistry*; D000941:Antigens / Q000737:chemistry*; D018360:Crystallography, X-Ray; D004581:Electronics / Q000379:methods; D007477:Ions / Q000737:chemistry; D009578:Nitrobenzenes / Q000737:chemistry*; D012680:Sensitivity and Specificity
D000814:Aniline Compounds; D000941:Antigens; D007477:Ions; D009578:Nitrobenzenes; C015384:nitramine