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Journal of Molecular Modeling

, Volume 17, Issue 10, pp 2569–2574 | Cite as

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

  • Miroslav Pospíšil
  • Pavel Vávra
  • Monica C. Concha
  • Jane S. Murray
  • Peter PolitzerEmail author
Original Paper

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.

Figure

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)

Keywords

Available free space Energetic compounds Impact sensitivity Molecular volumes Packing coefficients 

Notes

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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Copyright information

© Springer-Verlag 2011

Authors and Affiliations

  • Miroslav Pospíšil
    • 1
  • Pavel Vávra
    • 2
  • Monica C. Concha
    • 3
  • Jane S. Murray
    • 3
    • 4
  • Peter Politzer
    • 3
    • 4
    Email author
  1. 1.Faculty of Mathematics and PhysicsCharles UniversityPrague 2Czech Republic
  2. 2.Institute of Energetic Materials, Faculty of Chemical TechnologyUniversity of PardubicePardubiceCzech Republic
  3. 3.Department of ChemistryUniversity of New OrleansNew OrleansUSA
  4. 4.CleveTheoCompClevelandUSA

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