Thermal Decomposition of Condensed-Phase Nitromethane from Molecular Dynamics from ReaxFF Reactive Dynamics

Abstract

We studied the thermal decomposition and subsequent reaction of the energetic material nitromethane (CH_3NO_2) using molecular dynamics with ReaxFF, a first principles-based reactive force field. We characterize the chemistry of liquid and solid nitromethane at high temperatures (2000−3000 K) and density 1.97 g/cm^3 for times up to 200 ps. At T = 3000 K the first reaction in the decomposition of nitromethane is an intermolecular proton transfer leading to CH_3NOOH and CH_2NO_2. For lower temperatures (T = 2500 and 2000 K) the first reaction during decomposition is often an isomerization reaction involving the scission of the C−N bond the formation of a C−O bond to form methyl nitrate (CH_3ONO). Also at very early times we observe intramolecular proton transfer events. The main product of these reactions is H_2O which starts forming following those initiation steps. The appearance of H_2O marks the beginning of the exothermic chemistry. Recent quantum-mechanics-based molecular dynamics simulations on the chemical reactions and time scales for decomposition of a crystalline sample heated to T = 3000 K for a few picoseconds are in excellent agreement with our results, providing an important, direct validation of ReaxFF.

Group Members

William A. Goddard III

Charles and Mary Ferkel Professor