Hydrogen Transfer in Energetic Materials from ReaxFF and DFT Calculations

OV Sergeev and AV Yanilkin, JOURNAL OF PHYSICAL CHEMISTRY A, 121, 3019-3027 (2017).

DOI: 10.1021/acs.jpca.6b13088

Energetic materials are characterized by fast and complex chemical reactions. It makes them hardly available for kinetic experiments in relevant conditions and a good target for reactive molecular dynamics simulations. In this work, unimolecular and condensed-phase thermal decomposition Of pentaerythritol tetranitrate (PETN) are investigated by ReaxFF molecular dynamics. It is shown that the decomposition kinetics in condensed phase may be described with the activation barrier lower by a factor of 2 than that for isolated molecules. The effect of the intermolecular hydrogen transfer is revealed in condensed phase. Energetic barriers for hydrogen transfer in two energetic materials (methyl nitrate, which is a nitroester as well as PETN, and o-nitrotoluene) are studied with ReaxFF and DFT using nudged elastic band technique. The results indicate that ReaxFP gives significantly lower activation energy for intermolecular hydrogen transfer in nitroesters than different DFT approximations, which ,explains the molecular dynamics results for PETN.

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