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Sensitivity and the available free space per molecule in the unit cell

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Abstract

Invoking the known link between impact sensitivity and compressibility, we have expanded upon an earlier preliminary study of the significance of the available free space per molecule in the unit cell, ΔV. We express ΔV as Veff – Vint, where Veff corresponds to zero free space, Veff = molecular mass/density. Vint is the intrinsic gas phase molecular volume. We demonstrate that Vint can be appropriately defined as the volume enclosed by the 0.003 au contour of the molecule’s electronic density; this produces packing coefficients that have the range and average value found crystallographically. Measured impact sensitivities show an overall tendency to increase as ΔV becomes larger. For nitramines, the dependence upon ΔV is rather weak; we interpret this as indicating that a single overriding factor dominates their initiation mechanism, e.g., N-NO2 rupture. (An analogous situation appears to hold for many organic azides.) In addition to the conceptual significance of identifying ΔV as a factor in impact sensitivity, the present results allow rough estimates of relative sensitivities that are not known.

Impact sensitivities, h 50, plotted against available free space per molecule in the unit cell, ΔV, for 7 nitramines (left) and 14 non-nitramines (right)

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Acknowledgments

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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Authors and Affiliations

  1. Faculty of Mathematics and Physics, Charles University, Ke Karlovu 3, 12116, Prague 2, Czech Republic

    Miroslav Pospíšil

  2. Institute of Energetic Materials, Faculty of Chemical Technology, University of Pardubice, 53210, Pardubice, Czech Republic

    Pavel Vávra

  3. Department of Chemistry, University of New Orleans, New Orleans, LA, 70148, USA

    Monica C. Concha, Jane S. Murray & Peter Politzer

  4. CleveTheoComp, 1951 W. 26th Street, Suite 409, Cleveland, OH, 44113, USA

    Jane S. Murray & Peter Politzer

Authors
  1. Miroslav Pospíšil
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  2. Pavel Vávra
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  3. Monica C. Concha
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  4. Jane S. Murray
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  5. Peter Politzer
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Correspondence to Peter Politzer.

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Pospíšil, M., Vávra, P., Concha, M.C. et al. Sensitivity and the available free space per molecule in the unit cell. J Mol Model 17, 2569–2574 (2011). https://doi.org/10.1007/s00894-010-0953-8

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  • DOI: https://doi.org/10.1007/s00894-010-0953-8

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