Graduation Year


Document Type




Degree Granting Department


Major Professor

Ivan I. Oleynik, Ph.D.


Bimolecular collision, Uniaxial compression, Molecular dynamics, Explosives, Detonation


An understanding of the atomic-scale features of chemical and physical processes taking place behind the shockwave front will help in addressing some of the major challenges in energetic materials research. The high pressure shockwave environment can be simulated using computational techniques to predict mechanical and chemical properties of a shocked material. Density functional theory calculations were performed to investigate uniaxial compressions of diamond and both hydrostatic and uniaxial compressions of TATB and NEST-1. For diamond, we calculated shear stresses for uniaxial compressions in the , , and directions and discovered the anomalous elastic regime which is responsible for the significant delay of plastic deformation behind a shockwave. For TATB, the hydrostatic equation of state, bulk modulus, and equilibrium structure were calculated using an empirical van der Waals correction.

The principal stresses, shear stresses, and energy change per atom calculated for uniaxial compressions in the directions normal to the {001}, {010}, {011}, {100}, {101}, {110}, and {111} planes show highly anisotropic behavior. A similar study was performed for the newly synthesized energetic material NEST-1 in order to predict mechanical properties under uniaxial compression. From the similarities in the calculated principal stresses for each compression direction we conclude that NEST-1 is likely to exhibit relatively isotropic behavior as compared to other energetic materials. Finally, reactive molecular dynamics of shock-induced initiation chemistry in detonating PETN was investigated, using first-principles density functional theory, in order to identify the reaction mechanisms responsible for shock sensitivities in energetic materials.

The threshold collision velocity of initiation for each orientation was determined and correlated with available experimental data on shock sensitivity. The production of NO2 was found to be the dominant reaction pathway in every reactive case. The simulations show that the reactive chemistry of initiation occurs at very short time scales ~10E?¹³ s at highly non-equilibrium conditions, and is driven by dynamics rather than temperature.