We extend the reactive force field ReaxFF to describe the high energy nitramine RDX and use it with molecular dynamics (MD) to study its shock-induced chemistry. We studied shock propagation via nonequilibrium MD simulations at various collision velocities. We find that for high impact velocities (>6 km/s) the RDX molecules decompose and react to form a variety of small molecules in very short time scales (<3 ps). These products are consistent with those found experimentally at longer times. For lower velocities only NO2 is formed, also in agreement with experiments.

Gas phase hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) is a relatively stable molecule which releases a large amount of energy upon decomposition. Although gas-phase unimolecular decomposition experiments suggest at least two major pathways, there is no mechanistic understanding of the reactions involving RDX or other energetic molecules (such as HMX and TATB), used in applications ranging from automobile air bags to rocket propellants. For the unimolecular decomposition of RDX, we find three pathways: (i) concerted decomposition of the ring to form three CH 2 NNO 2 (M ) 74) molecules, and (ii) homolytic cleaVage of an NN bond to form NO 2 (M ) 46) plus RDR (M ) 176), which subsequently decomposes to form various products. Experimental studies suggest that the concerted pathway is dominant while theoretical calculations have suggested that the homolytic pathway might require significantly less energy. We report here a third pathway: (iii) successive HONO elimination to form 3 HONO (M ) 47) plus stable 1,3,5-triazine (TAZ) (M ) 81) with subsequent decomposition of HONO to HO (M ) 17) and NO (M ) 30) and at higher energies of TAZ into three HCN (M ) 27). We examined all three pathways using first principles quantum mechanics (B3LYP, density functional theory), including the barriers for all low-lying products. We find: A threshold at ∼40 kcal/mol for which HONO elimination leads to TAZ plus 3 HONO, while NN homolytic cleavage leads to RDR plus NO 2 , and the concerted pathway is not allowed; above ∼52 kcal/mol the TAZ of the HONO elimination pathway can decompose into 3 HCN while the HONO can decompose into HO + NO; above ∼60 kcal/mol the concerted pathway opens to form CH 2 NNO 2 ; at a threshold of ∼65 kcal/mol the RDR of the NN homolytic pathway can decompose into other products. These predictions are roughly consistent with previous experimental results and should be testable with new experiments. This should aid the development of a kinetic scheme to understand combustion and decomposition of solid-phase RDX and related energetic compounds (e.g., HMX).

To improve the mechanistic understanding of the possible decomposition in the gas phase of the energetic material HMX (octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine), we used ab initio calculations to determine the various unimolecular decomposition channels. We find three distinct mechanisms: (i) homolytic cleavage of N-N bond to form NO 2 (M ) 46) and HMR (M ) 250) which subsequently decomposes to form various products; (ii) successive HONO eliminations to give four HONO (M ) 47) plus a stable intermediate (M ) 108); (iii) O-migration from one of the NO 2 groups of HMX to neighboring C atom followed by the decomposition of intermediate (M ) 296) to INT222 (a ring-opened RDX structure) and MN-oring (M ) 74), which can undergo dissociation to smaller mass fragments. The decomposition scheme for HMX is similar to that for RDX presented earlier (J. Phys. Chem. A 2000Chem. A , 104, 2261, except that concerted decomposition of HMX to four MN (M ) 74) molecules is not a favorable decomposition pathway, whereas this pathway was found in RDX decomposition (both experimentally and theoretically). The formation of RDR-o in the N-N homolysis pathway 1 or the formation of INT222 in pathways 1 and 3 presents an unified mechanistic scheme for the decomposition of both of these nitramines. The HMX decomposition mechanism correlates with available condensed phase experimental results, but detailed comparison of the predicted gas phase energetics is not possible.

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A single phase molecular adduct, MgCl2·6CH3OH has been synthesized using MgCl2 and the simplest alcohol, methanol. Structural, spectroscopic, and morphological studies have been carried out for a better understanding of the single phase MgCl2·6CH3OH adduct. 13C CPMAS solid state NMR studies show all six methanol molecules are magnetically equivalent and present in a single environment around the Mg2+ center. Raman spectral analysis of the characteristic peak at 708 cm–1 substantiates octahedral coordination of six CH3OH molecules around Mg2+. Solid state 13C NMR measurements, made after heat treatment at different temperatures, have been utilized to understand the variations in CH3OH stoichiometry and coordination around Mg2+ with temperature. A titanated active catalyst, TiCl4 on MgCl2·6CH3OH, has also been synthesized and subjected to detailed characterizations. The active catalyst shows high surface area (102 m2/g) and mesoporosity. The titanated catalyst has been screened for ethylene polymerization reactions using different cocatalysts (R3Al; R= −CH3, −CH2CH3, and −CH2CH(CH3)2). A total of 7.25 kg of polyethylene per gram of catalyst has been obtained with Me3Al cocatalyst, which is six times higher in activity compared with commercial Me3Al/TiCl4/ MgCl2·6EtOH-supported catalyst. Although porosity influences the catalytic activity, other factors also seem to contribute to the total catalytic activity.