Modeling the Reactions of Energetic Materials in the Condensed Phase

Exploring the Photochemistry of Solid 1,1-Diamino-2,2-dinitroethylene (FOX-7) Spanning Simple Bond Ruptures, Nitro-to-Nitrite Isomerization, and Nonadiabatic Dynamics

“…An intimate understanding of the reaction mechanisms involved in the decomposition of molecular energetic materials such as the nitro-amine FOX-7 (1,1-diamino-2,2-dinitroethylene; Scheme ) and of the successive reactions of the radical fragments produced in these processes is imperative to predict the long-term stability (aging behavior), , explosion efficiency (performance), , and the sensitivity to heat and shock of energetic materials. − These insights are further invaluable to dispose of energetic materials safely under controlled conditions, to model the time dependence during the ignition stage of explosives, and to develop novel insensitive energetic materials . The investigation of these processes along with the consecutive reactions of the transient radicals represents a fundamental challenge for experimentalists, theoreticians, and modelers considering the nonequilibrium conditions under which these reactions often occur, as radicals can be born with excess kinetic and internal, i.e., rovibrational, energy and in excited electronic states .…”

“…An intimate understanding of the reaction mechanisms involved in the decomposition of molecular energetic materials such as the nitro-amine FOX-7 (1,1-diamino-2,2-dinitroethylene; Scheme 1) and of the successive reactions of the radical fragments produced in these processes is imperative to predict the long-term stability (aging behavior), 1,2 explosion efficiency (performance), 3,4 and the sensitivity to heat and shock of energetic materials. 5−11 These insights are further invaluable to dispose of energetic materials safely under controlled conditions, to model the time dependence during the ignition stage of explosives, and to develop novel insensitive energetic materials.…”

Lyman α photolysis of solid nitromethane (CH3NO2) and D3-nitromethane (CD3NO2) – untangling the reaction mechanisms involved in the decomposition of model energetic materials

“…These involve the use as monopropellants, [1][2][3] liquid explosives, [4][5][6][7][8][9] and highperformance fuel additives for internal combustion engines as well as in pulsed detonation engines. 10 An understanding of the reaction mechanisms involved in the decomposition of nitromethane and of the successive reactions of the carbon-, nitrogen-, and oxygen-centered radical fragments produced in this process is imperative to predict the long-term stability (aging behavior), 11,12 the explosion efficiency (performance), 13,14 and the sensitivity of energetic materials to heat and shocks. 12,[15][16][17][18][19][20][21][22][23] Due to these implications, the decomposition mechanisms of nitromethane (CH 3 NO 2 ) have been extensively explored under collisionless conditions in the gas phase [24][25][26][27][28][29][30][31][32][33][34] exploiting infrared multi photon dissociation (IRMPD) and ultraviolet photodissociation (UVPD) both theoretically and experimentally for the last 30 years (Table 1, Fig.…”

Novel Reaction Mechanisms Pathways in the Electron Induced Decomposition of Solid Nitromethane (CH3NO2) and D3-Nitromethane (CD3NO2)

“…Nitromethane (CH 3 NO 2 ) is considered as a model of nitrohydrocarbon-based (RNO 2 ) energetic material covering propellants, , explosives, − and high-performance fuel additives for internal combustion engines and detonation systems . Here, an intimate knowledge of the pathways in the (unimolecular) decomposition of nitromethane and of the succeeding reactions of the radicals formed in this process is crucial to foretell the aging behavior, , performance, , and the sensitivity to heat and shock of energetic materials. ,− These insights are further invaluable to dispose energetic materials safely under controlled conditions, to model the time-dependence during the ignition stage of explosives, and to develop novel insensitive energetic materials. The investigation of these decomposition processes still represents a substantial challenge for experimentalists, theoreticians, and modelers , considering the nonequilibrium conditions under which these reactions often occur. − …”

“…Nitromethane (CH 3 NO 2 ) is considered as a model of nitrohydrocarbon-based (RNO 2 ) energetic material covering propellants, 1,2 explosives, 3−6 and high-performance fuel additives for internal combustion engines and detonation systems. 7 Here, an intimate knowledge of the pathways in the (unimolecular) decomposition of nitromethane and of the succeeding reactions of the radicals formed in this process is crucial to foretell the aging behavior, 8,9 performance, 10,11 and the sensitivity to heat and shock of energetic materials. 9,12−20 These insights are further invaluable to dispose energetic materials safely under controlled conditions, to model the timedependence during the ignition stage of explosives, and to develop novel insensitive energetic materials.…”