Thermal Decomposition of Condensed-Phase Nitromethane from Molecular Dynamics from ReaxFF Reactive Dynamics

We studied the thermal decomposition and subsequent reaction of the energetic material nitromethane (CH_3NO_2) using molecular dynamics with ReaxFF, a first principles-based reactive force field. We characterize the chemistry of liquid and solid nitromethane at high temperatures (2000−3000 K) and density 1.97 g/cm^3 for times up to 200 ps. At T = 3000 K the first reaction in the decomposition of nitromethane is an intermolecular proton transfer leading to CH_3NOOH and CH_2NO_2. For lower temperatures (T = 2500 and 2000 K) the first reaction during decomposition is often an isomerization reaction involving the scission of the C−N bond the formation of a C−O bond to form methyl nitrate (CH_3ONO). Also at very early times we observe intramolecular proton transfer events. The main product of these reactions is H_2O which starts forming following those initiation steps. The appearance of H_2O marks the beginning of the exothermic chemistry. Recent quantum-mechanics-based molecular dynamics simulations on the chemical reactions and time scales for decomposition of a crystalline sample heated to T = 3000 K for a few picoseconds are in excellent agreement with our results, providing an important, direct validation of ReaxFF

High On/Off Ratio Graphene Nanoconstriction Field Effect Transistor

We report a method to pattern monolayer graphene nanoconstriction field effect transistors (NCFETs) with critical dimensions below 10 nm. NCFET fabrication is enabled by the use of feedback controlled electromigration (FCE) to form a constriction in a gold etch mask that is first patterned using conventional lithographic techniques. The use of FCE allows the etch mask to be patterned on size scales below the limit of conventional nanolithography. We observe the opening of a confinement-induced energy gap as the NCFET width is reduced, as evidenced by a sharp increase in the NCFET on/off ratio. The on/off ratios we obtain with this procedure can be larger than 1000 at room temperature for the narrowest devices; this is the first report of such large room temperature on/off ratios for patterned graphene FETs.Comment: 18 pages, 6 figures, to appear in Smal

Initial Chemical Events in the Energetic Material RDX under Shock Loading: Role of Defects

We use the recently developed reactive force field ReaxFF with molecular dynamics (MD) to study the role of voids on the initial chemical events in the high-energy material RDX under shock loading. We find that for strong shocks (particles velocity of 3 km/s) very small gaps (2 nm) lead to important over-heating (~ 1000 K). This over-heating facilitates chemical reactions and leads to a larger production of small molecules (such as NO2, NO, OH) than in perfect crystals shocked with the same strength. The chemical reactions occur after the void has collapsed and the ejected material re-compressed rather than when hot molecules are ejected out of the downstream surface

Series of experiments for empirical validation of solar gain modelling in building energy simulation codes - experimental setup, test cell characterization, specifications and uncertainty analysis

Empirical validation of building energy simulation codes is an important component in understanding the capacity and limitations of the software. Within the framework of Task 34/Annex 43 of the International Energy Agency (IEA), a series of experiments was performed in an outdoor test cell. The objective of these experiments was to provide a high-quality data set for code developers and modelers to validate their solar gain models for windows with and without shading devices. A description of the necessary specifications for modeling these experiments is provided in this paper, which includes information about the test site location, experimental setup, geometrical and thermophysical cell properties including estimated uncertainties. Computed overall thermal cell properties were confirmed by conducting a steady-state experiment without solar gains. A transient experiment, also without solar gains, and corresponding simulations from four different building energy simulation codes showed that the provided specifications result in accurate thermal cell modeling. A good foundation for the following experiments with solar gains was therefore accomplished

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

Empirical validation of models to compute solar irradiance on inclined surfaces for building energy simulation

Accurately computing solar irradiance on external facades is a prerequisite for reliably predicting thermal behavior and cooling loads of buildings. Validation of radiation models and algorithms implemented in building energy simulation codes is an essential endeavor for evaluating solar gain models. Seven solar radiation models implemented in four building energy simulation codes were investigated: (1) isotropic sky, (2) Klucher, (3) Hay-Davies, (4) Reindl, (5) Muneer, (6) 1987 Perez, and (7) 1990 Perez models. The building energy simulation codes included: EnergyPlus, DOE-2.1E, TRNSYS-TUD, and ESP-r. Solar radiation data from two 25 days periods in October and March/April, which included diverse atmospheric conditions and solar altitudes, measured on the EMPA campus in a suburban area in Duebendorf, Switzerland, were used for validation purposes. Two of the three measured components of solar irradiances - global horizontal, diffuse horizontal and direct-normal - were used as inputs for calculating global irradiance on a south-west façade. Numerous statistical parameters were employed to analyze hourly measured and predicted global vertical irradiances. Mean absolute differences for both periods were found to be: (1) 13.7% and 14.9% for the isotropic sky model, (2) 9.1% for the Hay-Davies model, (3) 9.4% for the Reindl model, (4) 7.6% for the Muneer model, (5) 13.2% for the Klucher model, (6) 9.0%, 7.7%, 6.6%, and 7.1% for the 1990 Perez models, and (7) 7.9% for the 1987 Perez model. Detailed sensitivity analyses using Monte Carlo and fitted effects for N-way factorial analyses were applied to assess how uncertainties in input parameters propagated through one of the building energy simulation codes and impacted the output parameter. The implications of deviations in computed solar irradiances on predicted thermal behavior and cooling load of buildings are discussed

Logarithmic deformations of the rational superpotential/Landau-Ginzburg construction of solutions of the WDVV equations

The superpotential in the Landau-Ginzburg construction of solutions to the Witten-Dijkgraaf-Verlinde-Verlinde (or WDVV) equations is modified to include logarithmic terms. This results in deformations - quadratic in the deformation parameters- of the normal prepotential solutions of the WDVV equations. Such solutions satisfy various pseudo-quasi-homogeneity conditions, on assigning a notional weight to the deformation parameters. These solutions originate in the so-called `water-bag' reductions of the dispersionless KP hierarchy. This construction includes, as a special case, deformations which are polynomial in the flat coordinates, resulting in a new class of polynomial solutions of the WDVV equations

Limitation of energy deposition in classical N body dynamics

Energy transfers in collisions between classical clusters are studied with Classical N Body Dynamics calculations for different entrance channels. It is shown that the energy per particle transferred to thermalised classical clusters does not exceed the energy of the least bound particle in the cluster in its ``ground state''. This limitation is observed during the whole time of the collision, except for the heaviest system.Comment: 13 pages, 15 figures, 1 tabl

Effects of Self-field and Low Magnetic Fields on the Normal-Superconducting Phase Transition

Researchers have studied the normal-superconducting phase transition in the high-$T_c$ cuprates in a magnetic field (the vortex-glass or Bose-glass transition) and in zero field. Often, transport measurements in "zero field" are taken in the Earth's ambient field or in the remnant field of a magnet. We show that fields as small as the Earth's field will alter the shape of the current vs. voltage curves and will result in inaccurate values for the critical temperature $T_c$ and the critical exponents $\nu$ and $z$, and can even destroy the phase transition. This indicates that without proper screening of the magnetic field it is impossible to determine the true zero-field critical parameters, making correct scaling and other data analysis impossible. We also show, theoretically and experimentally, that the self-field generated by the current flowing in the sample has no effect on the current vs. voltage isotherms.Comment: 4 pages, 4 figure