Electronic excitations in shocked nitromethane

The nature of electronic excitations in crystalline solid nitromethane under conditions of shock loading and static compression are examined. Density-functional theory calculations are used to determine the crystal bandgap under hydrostatic stress, uniaxial strain, and shear strain. Bandgap lowering under uniaxial strain due to molecular defects and vacancies is considered. Ab initio molecular-dynamics simulations are done of all possible nearest-neighbor collisions at a shock front, and of crystal shearing along a sterically hindered slip plane. In all cases, the bandgap is not lowered enough to produce a significant population of excited states in the crystal. The nearly free rotation of the nitromethane methyl group and localized nature of the highest occupied molecular orbital and lowest unoccupied molecular orbital states play a role in this result. Dynamical effects have a more significant effect on the bandgap than static effects, but relative molecule velocities in excess of 6 km/s are required to produce a significant thermal population of excited states.