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J Phys Chem A. 2011 Aug 18;115(32):9055-68. doi: 10.1021/jp204562d. Epub 2011 Jul 28.

Topological analysis of the molecular charge density and impact sensitivy models of energetic molecules.

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Departamento de Química, Instituto Militar de Engenharia, Praça General Tibúrcio, 80, Rio de Janeiro - Rj, 22290-270, Brazil.


Important explosives of practical use are composed of nitroaromatic molecules. In this work, we optimized geometries and calculated the electron density of 17 nitroaromatic molecules using the Density Functional Theory (DFT) method. From the DFT one-electron density matrix, we computed the molecular charge densities, thus the electron densities, which were then decomposed into electric multipoles located at the atomic sites of the molecules using the distributed multipole analysis (DMA). The multipoles, which have a direct chemical interpretation, were then used to analyze in details the ground state charge structure of the molecules and to seek for correlations between charge properties and sensitivity of the corresponding energetic material. The DMA multipole moments do not present large variations when the size of the Gaussian basis set is changed; the largest variations occurred in the range 10-15% for the dipole and quadrupole moments of oxygen atoms. The charges on the carbon atoms of the aromatic ring of each molecule become more positive when the number of nitro groups increases and saturate when there are five and six nitro groups. The magnitude and the direction of the dipole moments of the carbon atoms, indicators of site polarization, also depend on the nature of adjacent groups, with the largest dipole value being for C-H bonds. The total magnitude of the quadrupole moment of the aromatic ring carbon atoms indicates a decrease in the delocalized electron density due to an electron-withdrawing effect. Three models for sensitivity of the materials based on the DMA multipoles were proposed. Explosives with large delocalized electron densities in the aromatic ring of the component molecule, expressed by large quadrupole values on the ring carbon atoms, correspond to more insensitive materials. Furthermore, the charges on the nitro groups also influence the impact sensitivity.


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