A possible crystal volume factor in the impact sensitivities of some energetic compounds

AbstractWe 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. FigureMeasured impact sensitivities (h50) plotted against computed ΔV for the compounds in Table 1. Triangles correspond to nitramines, circles to all others

[1]  R. Stewart.  On the mapping of electrostatic properties from bragg diffraction data , 1979 .

[2]  M. J. Kamlet,et al.  The relationship of Impact Sensitivity with Structure of Organic High Explosives. II. Polynitroaromatic explosives , 1979 .

[3]  Peter Politzer,et al.  Chemical Applications of Atomic and Molecular Electrostatic Potentials: "Reactivity, Structure, Scattering, And Energetics Of Organic, Inorganic, And Biological Systems" , 2013 .

[4]  Thermal decomposition of energetic materials. Part 9. A relationship of molecular structure and vibrations to decomposition: polynitro-3,3,7,7-tetrakis(trifluoromethyl)-2,4,6,8-tetraazabicyclo[3.3.0]octanes , 1986 .

[5]  Cheng Chang,et al.  Properties of atoms in molecules: atomic volumes , 1987 .

[6]  Arthur Greenberg,et al.  Structure and reactivity , 1988 .

[7]  T. Brill,et al.  Thermal Decomposition of Energetic Materials XXVIII. Predictions and results for nitramines of bis‐imidazolidinedione: DINGU, TNGU and TDCD , 1988 .

[8]  Molecular beam-sampled laser pyrolysis of dimethylnitramine , 1989 .

[9]  Structural basis of the impact sensitivities of 1-picryl-1,2,3-triazole, 2-picryl-1,2,3-triazole, 4-nitro-1-picryl-1,2,3-triazole, and 4-nitro-2-picryl-1,2,3-triazole , 1989 .

[10]  S. Bulusu.  Chemistry and physics of energetic materials , 1990 .

[11]  J. Murray,et al.  Shock-sensitivity relationships for nitramines and nitroaliphatics , 1991 .

[12]  A. Imamura,et al.  A molecular orbital study on the effects of electron correlation on the unique NN bond in nitramines , 1993 .

[13]  T. Brill,et al.  Kinetics and mechanisms of thermal decomposition of nitroaromatic explosives , 1993 .

[14]  A. Imamura,et al.  A relationship between the impact sensitivity and the electronic structures for the unique NN bond in the HMX polymorphs , 1994 .

[15]  J. Murray,et al.  C-NO2 dissociation energies and surface electrostatic potential maxima in relation to the impact sensitivities of some nitroheterocyclic molecules , 1995 .

[16]  J. Murray,et al.  Relationships between impact sensitivities and molecular surface electrostatic potentials of nitroaromatic and nitroheterocyclic molecules , 1995 .

[17]  Kazuyoshi Ueda,et al.  Molecular Dynamics Simulations of Initial Decomposition Process on the Unique N−N Bond in Nitramines in the Crystalline State , 1996 .

[18]  J. Murray,et al.  Relationships between dissociation energies and electrostatic potentials of CNO2 bonds: applications to impact sensitivities , 1996 .

[19]  P. Politzer,et al.  Density functional analysis of a decomposition of 4‐nitro‐1,2,3‐triazole through the evolution of N2 , 1997 .

[20]  J. Murray,et al.  Statistical analysis of the molecular surface electrostatic potential: an approach to describing noncovalent interactions in condensed phases , 1998 .

[21]  J. Murray,et al.  Effects of strongly electron-attracting components on molecular surface electrostatic potentials: application to predicting impact sensitivities of energetic molecules , 1998 .

[22]  J. Karle,et al.  Proposed Mechanism of 1,1-Diamino-Dinitroethylene Decomposition: A Density Functional Theory Study , 1999 .

[23]  Ab Initio Study of Unimolecular Decomposition of Nitroethylene , 1999 .

[24]  J. Murray,et al.  Computational prediction of condensed phase properties from statistical characterization of molecular surface electrostatic potentials , 2001 .

[25]  B. Rice,et al.  A quantum mechanical investigation of the relation between impact sensitivity and the charge distribution in energetic molecules , 2002 .

[26]  Peter Politzer,et al.  The fundamental nature and role of the electrostatic potential in atoms and molecules , 2002 .

[27]  Decomposition, crystal, and molecular properties , 2003 .

[28]  Y. Shu,et al.  Investigation of correlation between impact sensitivities and nitro group charges in nitro compounds. , 2005, The journal of physical chemistry. B.

[29]  X. Gong,et al.  Crystal density predictions for nitramines based on quantum chemistry. , 2007, Journal of hazardous materials.

[30]  B. Rice,et al.  Accurate predictions of crystal densities using quantum mechanical molecular volumes. , 2007, The journal of physical chemistry. A.

[31]  Svatopluk Zeman,et al.  Sensitivities of High Energy Compounds , 2007 .

[32]  J. Murray,et al.  Computational determination of effects of electric fields upon , 2009 .

[33]  Peter Politzer,et al.  Expansion of the σ-hole concept , 2009, Journal of molecular modeling.

[34]  Monica C. Concha,et al.  An electrostatic interaction correction for improved crystal density prediction , 2009 .

[35]  J. Murray,et al.  Computed effects of electric fields upon the CNO2 and NNO2 bonds of nitromethane and dimethylnitramine , 2009 .

[36]  Peter Politzer,et al.  Links between surface electrostatic potentials of energetic molecules, impact sensitivities and C–NO2/N–NO2 bond dissociation energies , 2009 .

[37]  J. Murray,et al.  Reaction force analyses of nitro-aci tautomerizations of trinitromethane, the elusive trinitromethanol, picric acid and 2,4-dinitro-1H-imidazole , 2009 .

[38]  Siddharth Dasgupta,et al.  Explanation of the colossal detonation sensitivity of silicon pentaerythritol tetranitrate (Si-PETN) explosive. , 2009, Journal of the American Chemical Society.