Question

Correction of the reaxff reactive force field for london dispersion, with applications to the equations of state for energetic materials,

Answer 1

The practical levels of density functional theory (DFT) for solids (LDA, PBE, PW91, B3LYP) are well-known not to account adequately for the London dispersion (van der Waals attraction) so important in molecular solids, leading to equilibrium volumes for molecular crystals ∼10–15% too high. The ReaxFF reactive force field is based on fitting such DFT calculations and suffers from the same problem. In the paper we extend ReaxFF by adding a London dispersion term with a form such that it has low gradients (lg) at valence distances leaving the already optimized valence interactions intact but behaves as 1/R6 for large distances. We derive here these lg corrections to ReaxFF based on the experimental crystal structure data for graphite, polyethylene (PE), carbon dioxide, and nitrogen and for energetic materials: hexahydro-1,3,5-trinitro-1,3,5-s-triazine (RDX), pentaerythritol tetranitrate (PETN), 1,3,5-triamino-2,4,6-trinitrobenzene (TATB), and nitromethane (NM). After this dispersion correction the average error of predicted equilibrium volumes decreases from 18.5 to 4.2% for the above systems. We find that the calculated crystal structures and equation of state with ReaxFF-lg are in good agreement with experimental results. In particular, we examined the phase transition between α-RDX and γ-RDX, finding that ReaxFF-lg leads to excellent agreement for both the pressure and volume of this transition occurring at ∼4.8 GPa and ∼2.18 g/cm3 density from ReaxFF-lg vs 3.9 GPa and ∼2.21 g/cm3 from experiment. We expect ReaxFF-lg to improve the descriptions of the phase diagrams for other energetic materials.