Molecular Dynamics Simulations of Detonation Instability

After making modifications to the Reactive Empirical Bond Order potential for Molecular Dynamics (MD) of Brenner et al. in order to make the model behave in a more conventional manner, we discover that the new model exhibits detonation instability, a first for MD. The instability is analyzed in terms of the accepted theory.Comment: 7 pages, 6 figures. Submitted to Phys. Rev. E Minor edits. Removed parenthetical statement about P^\nu from conclusion

Thermal decomposition of RDX from reactive molecular dynamics

We use the recently developed reactive force field ReaxFF with molecular dynamics to study thermal induced chemistry in RDX [cyclic-[CH2N(NO2)]3] at various temperatures and densities. We find that the time evolution of the potential energy can be described reasonably well with a single exponential function from which we obtain an overall characteristic time of decomposition that increases with decreasing density and shows an Arrhenius temperature dependence. These characteristic timescales are in reasonable quantitative agreement with experimental measurements in a similar energetic material, HMX [cyclic-[CH2N(NO2)]4]. Our simulations show that the equilibrium population of CO and CO2 (as well as their time evolution) depend strongly of density: at low density almost all carbon atoms form CO molecules; as the density increases larger aggregates of carbon appear leading to a C deficient gas phase and the appearance of CO2 molecules. The equilibrium populations of N2 and H2O are more insensitive with respect to density and form in the early stages of the decomposition process with similar timescales

Simulations on the Thermal Decomposition of a Poly(dimethylsiloxane) Polymer Using the ReaxFF Reactive Force Field

To investigate the failure of the poly(dimethylsiloxane) polymer (PDMS) at high temperatures and pressures and in the presence of various additives, we have expanded the ReaxFF reactive force field to describe carbon−silicon systems. From molecular dynamics (MD) simulations using ReaxFF we find initial thermal decomposition products of PDMS to be CH_3 radical and the associated polymer radical, indicating that decomposition and subsequent cross-linking of the polymer is initiated by Si−C bond cleavage, in agreement with experimental observations. Secondary reactions involving these CH_3 radicals lead primarily to formation of methane. We studied temperature and pressure dependence of PDMS decomposition by following the rate of production of methane in the ReaxFF MD simulations. We tracked the temperature dependency of the methane production to extract Arrhenius parameters for the failure modes of PDMS. Furthermore, we found that at increased pressures the rate of PDMS decomposition drops considerably, leading to the formation of fewer CH_3 radicals and methane molecules. Finally, we studied the influence of various additives on PDMS stability. We found that the addition of water or a SiO_2 slab has no direct effect on the short-term stability of PDMS, but addition of reactive species such as ozone leads to significantly lower PDMS decomposition temperature. The addition of nitrogen monoxide does not significantly alter the degradation temperature but does retard the initial production of methane and C_2 hydrocarbons until the nitrogen monoxide is depleted. These results, and their good agreement with available experimental data, demonstrate that ReaxFF provides a useful computational tool for studying the chemical stability of polymers

Bridging properties of multiblock copolymers.

Using self-consistent field theory, we attempt to elucidate the links between microscopically determined properties, such as the bridging fraction of chains, and mechanical properties of multiblock copolymer materials. We determine morphological aspects such as period and interfacial width and calculate the bridging fractions, and compare with experimental data

Model-free test of local-density mean-field behavior in electric double layers

We derive a self-similarity criterion that must hold if a planar electric double layer (EDL) can be captured by a local-density approximation (LDA), without specifying any specific LDA. Our procedure generates a similarity coordinate from EDL profiles (measured or computed), and all LDA EDL profiles for a given electrolyte must collapse onto a master curve when plotted against this similarity coordinate. Noncollapsing profiles imply the inability of any LDA theory to capture EDLs in that electrolyte. We demonstrate our approach with molecular simulations, which reveal dilute electrolytes to collapse onto a single curve, and semidilute ions to collapse onto curves specific to each electrolyte, except where size-induced correlations arise. © 2013 American Physical Society