Sylke Boyd

Nonreactive molecular dynamics force field for crystalline hexahydro-1,3,5-trinitro-1,3,5 triazine

An empirical nonreactive force field has been developed for molecular dynamics (MD)/Monte Carlo simulation of the formation, diffusion, and agglomeration of point defects in the crystal lattice of the alpha modification of hexahydro-1,3,5-trinitro-1,3,5 triazine (RDX) using flexible molecules. Bond stretching and angle bending are represented by Morse and harmonic functions, and torsion by a truncated cosine series. Nonbonded interactions, both inter- and intramolecular, are described by Buckingham potentials separately parametrized. Intermolecular electrostatic interactions are treated via a Coulomb term coupled with a smooth 15.0 A cutoff radius. Parameters were taken in part from earlier published works and were determined partly by fitting to known molecular and crystal properties of RDX. In MD simulations at constant pressure and temperature, the model was able to stabilize and maintain the correct crystal structure, symmetry, and molecular conformation of alpha-RDX. Vibrational frequencies, lattice binding energy and dimensions, coefficients of thermal expansion, and several unusually short intermolecular distances are all reproduced in satisfactory agreement with experimental data.

Density Functional Tight-Binding Studies of Carbon Nanotube Structures

A density functional tight-binding self-consistent charge approach has been used to study the structures and elastic properties of nine model carbon nanotubes of different helicities and diameters between 5.5 and 10.8 A. The systems contain from 112 to 268 atoms and were optimized under periodic boundary conditions in the axial direction. Both the carbon networks and the overall tube dimensions were optimized. Most of the C—C bond lengths are slightly lengthened relative to graphene (two-dimensional graphite); the others remain essentially the same or are shorter. There is overall a longitudinal compression of the tube. The strain energy per atom, relative to graphene, varies inversely with the square of the tube radius. The Youngs moduli decrease with increasing radius but do not depend upon chirality. The Poisson ratios are nearly constant. The consequences of removing an electron from each system were also investigated. In most instances, the tube dimensions were little affected; in only a few cases is there a change in length or radius (positive or negative) as large as 0.10%. The Youngs moduli remain the same as for the neutral systems, but the Poisson ratios tend to increase for metals and semimetals and to decrease for semiconductors.

Molecular Dynamics Simulations of Energetic Solids

A continuing objective in the area of energetic materials is to reduce sensitivity toward impact and shock. One approach is to develop a better understanding of how factors related to the crystal lattice, e.g., defects, influence the initiation and propagation of detonation. Molecular dynamics is a useful tool for this purpose. This paper presents an overview of molecular dynamics treatments of energetic solids. Some of these have simulated initiation and propagation in idealized systems; others have focused on developing a satisfactory procedure for describing molecular crystals of practical significance. Our emphasis in this discussion is on the progress that has been made along the second lines.

Molecular dynamics characterization of void defects in crystalline (1,3,5-trinitro-1,3,5-triazacyclohexane)

In the context of a continuing investigation of factors that affect the sensitivities of energetic materials to detonation initiation, we have carried out a molecular dynamics characterization of void defects in crystalline (1,3,5-trinitro-1,3,5-triazacyclo-hexane). An empirical force field that is capable of handling flexible molecules in a pliable crystal was used. Voids ranging in size from 2 to 30 adjacent vacated sites were created in model lattices of 216 or 512 molecules. Energetic and geometric ground state properties were determined. The void formation energy per molecule removed was found to decrease from 50 kcal/mol for a single vacancy to about 23+/-2 kcal/mol for voids larger than one unit cell (8 molecules). Analysis of the local binding energies in the vicinity of a void reveals not only the expected decrease for molecules directly on the void surface but also a wide spread of values in the first 5-10 A away from the surface; this includes some molecules with local binding energies significantly higher than in the defect-free lattice. Molecular conformational changes and reorientations begin to be found in the vicinities of voids larger than one unit cell. Thermal behavior investigated includes void and molecular diffusion coefficients and fluctuations in void size.