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We performed a series of six plate impact experiments on polyimide and modeled them using new reactant and products equations of state combined with an Arrhenius rate model. The first experiment was diagnosed with embedded electromagnetic velocity gauges through which we directly observed attenuation of the lead shock to an approximately constant state over a propagation distance of roughly 4 mm. Simulated gauge profiles were in excellent qualitative agreement with experiment and suggested a sluggish chemical reaction that did not proceed to completion. The remaining five experiments were conducted in a transmission geometry and diagnosed velocimetrically at the sample/window interface. All five of these yielded profiles with a sharp shock followed by a more gradual approach to maximum interface velocity that was "rounded" to varying degree. These profiles proved difficult to interpret unambiguously due to the convolution of the reactive wave upon first shock with reflection of the lead wave and reshock or release by the window. Comparison with thermochemical calculations strongly suggests that the point of maximum interface velocity corresponds to the equilibrium reshock or release locus. We discuss the implications of this point for the practice of impedance matching based on the reflected Hugoniot of reactive materials such as polymers. The reactant and thermochemical products equations of state are developmental SESAME tables 97710 and 97720, respectively. [ABSTRACT FROM AUTHOR]

We present new equations of state (EOS) for polymethylmethacrylate and its shock-driven decomposition products, generated in both tabular form and as linear U S − u p fits to all previously available shock data. Different approaches are taken for materials shocked above and below the apparent threshold for chemical reactions at pressures P ≈ 30 GPa. Both EOSs are calibrated to and compared with a broad array of experimental results, as well as new ab initio molecular dynamics simulations presented here. Comparisons are good in most cases, and we focus our particular attention on those observables that test the distinction between reactants and products. [ABSTRACT FROM AUTHOR]

This paper describes the calibration of the Arrhenius Wescott–Stewart–Davis (AWSD) reactive flow model for the recently developed high explosive PBX 9701, which consists of 97% 3, 3 ′ -diamino-4, 4 ′ -azoxyfurazan (DAAF) and 3% FK-800 binder by weight. DAAF-based explosive formulations have several desirable qualities as they are relatively insensitive to non-shock insults but have higher performance than triaminotrinitrobenzene based formulations. Equations of state for the explosive reactants and products are calibrated using a combination of existing and new experimental data and theoretical calculations. The AWSD rate law calibration utilizes both one-dimensional shock-to-detonation and multidimensional rate stick experiments to capture the shock initiation and propagating detonation regimes. Validation of the calibrated model is demonstrated through comparison with recent gas-gun experiments. [ABSTRACT FROM AUTHOR]

Polysulfone was shock loaded to pressures of 14.6–26.2 GPa in a series of gas gun-driven plate-impact experiments measuring material response with embedded electro-magnetic particle velocity gauges and optical velocimetry. The embedded electro-magnetic particle velocity gauges did not show a distinct two-wave structure but did show rounding that suggested a reaction but not a distinct separation of the reactants and product waves. In contrast, the transmission experiments fielded with optical velocimetry, with product pressures ranging from 21.0 to 26.2 GPa, showed well-defined two-wave structures due to shock-driven chemical decomposition of the polymer to products at a higher density. Distinct two-wave structures have not previously been published in literature during polymer compression; here, we observed these two-wave structures at both the polymer/lithium fluoride and polymer/polymethylmethacrylate interfaces. Hydrodynamic simulations of the experiments were performed using a newly constructed SESAME equation of state (EOS) for the polymer, a thermochemical EOS for the decomposition products, and an Arrhenius reaction rate model for the kinetics of the reaction. Simulation results also demonstrated two-wave structures but were unable to quantitatively reproduce either the embedded gauge or optical velocimetry data. [ABSTRACT FROM AUTHOR]

We construct new equations of state (EOS) for high density and ultrahigh molecular weight polyethylene and their chemical decomposition products under shock loading. The former were built using the SESAME framework, based in part on new specific heat and thermal expansion data reported here. The products EOS was based on thermochemical modeling under the assumption of full thermodynamic and chemical equilibrium. The products are represented as the ideal mixture of bulk carbon in the form of diamond, H 2 , H, and CH 4. In the process of building a new EOS for the products, we recalibrated our exponential-6 pair potential for methane in order to better agree with data that have appeared since its original parameterization. The polyethylene EOS were calibrated to thermal, thermomechanical, and shock data, and their performance was evaluated in hydrodynamic modeling of deep release experiments reported previously. [ABSTRACT FROM AUTHOR]

We performed a series of plate impact experiments on NH3 gas initially at room temperature and at a pressure of ∼100 psi. Shocked states were determined by optical velocimetry and the temperatures by optical pyrometry, yielding compression ratios of ∼5–10 and second shock temperatures in excess of 7500 K. A first-principles statistical mechanical (thermochemical) approach that included chemical dissociation yielded reasonable agreement with experimental results on the principal Hugoniot, even with interparticle interactions neglected. Theoretical analysis of reshocked states, which predicts a significant degree of chemical dissociation, showed reasonable agreement with experimental data for higher temperature shots; however, reshock calculations required the use of interaction potentials. We rationalize the very different shock temperatures obtained, relative to previous results for argon, in terms of atomic versus molecular heat capacities. [ABSTRACT FROM AUTHOR]

A new method is described for optimizing minimal energy conical intersection (MECI), which is based on a sequential penalty constrained optimization in conjunction with a smoothing function. This method is applied for optimizing the MECI geometries by using the multistate formulation of second-order multireference perturbation theory (MS-CASPT2).

We present the first application of reactive Monte Carlo in a first-principles context. The algorithm samples in a modified NVT ensemble in which the volume, temperature, and total number of atoms of a given type are held fixed, but molecular composition is allowed to evolve through stochastic variation of chemical connectivity. We discuss general features of the method, as well as techniques needed to enhance the efficiency of Boltzmann sampling. Finally, we compare the results of simulation of NH3 to those of ab initio molecular dynamics (AIMD).We find that there are regions of state space for which RxMC sampling is much more efficient than AIMD due to the "rare-event" character of chemical reactions. [ABSTRACT FROM AUTHOR]

Shock compression of two molded, carbon fiber-filled polymer composites was performed in gas gun-driven plate impact experiments at impact velocities up to ≈5 km/s. Hugoniot states for both composites were obtained from <5GPa to nearly 50GPa. The two materials contained a high fill percentage of chopped carbon fibers, bound by either phenolic or cyanate ester polymeric resins. Their dynamic responses were similar, although the 10wt.% difference of carbon fill produced measureable divergence in shock compressibility. The chopped carbon fibers in the polymer matrix led to moderately anisotropic shocks, particularly when compared with the more commonly encountered filament-wound carbon fiber-epoxy composites. A discontinuity, or cusp, was observed in the principal Hugoniot of both materials near 25GPa. We attribute the accompanying volume collapse to shock-driven chemical decomposition above this condition. Inert and reacted products equations of state were used to capture the response of the two materials below and above the cusp. [ABSTRACT FROM AUTHOR]

We present the results of plate impact experiments performed on 30%-75% porous, polymeric methylene diphenyl diisocyanate polyurethane foams. The combination of new data with those previously obtained on full-density material was used to calibrate complete equations-of-state under both inert and chemically reactive frameworks. Description of unreacted polyurethane was based on a combination of Hayes and P-α models, whereas its decomposition products were predicted via free energy minimization under the assumption of chemical and thermodynamic equilibrium. Correspondence of experiment and theory suggests that polyurethane at all densities decomposes when shocked above some threshold pressure, and that this threshold falls dramatically as a function of initial porosity. The shock locus of foams at 50% or less of theoretical maximum density was found "anomalous" in the sense that final volumes increased with pressure. We attribute this anomaly to chemical decomposition of the initial matrix to a mixture of small-molecule fluids and bulk carbon (graphite or diamond, depending on the initial density). [ABSTRACT FROM AUTHOR]

The low- and high-strain-rate compaction response of three distinct morphology CeO2 powders was measured experimentally. At low-strain-rates, the compression path was found to vary with initial particle morphology as a result of differences in initial packing structure and particle rearrangement at low stresses. However, similar compression responses were observed at higher stresses under low-strain-rate loading. Dynamic experiments were performed at impact velocities between 0.15 and 0.78 km/s, and resulted in compaction stresses of 0.51-4.59 GPa in the powders. In contrast to the behavior observed at low stresses and low-strain-rates, dynamic loading resulted in a similar compaction response for all morphology powders. The dynamic results were treated with a Hayes equation of state augmented with a P-α compaction model, and good agreement between experimental and theoretical results was achieved. From the observed similarities in compressibility for the three morphology powders at elevated stresses at both low- and high-strain-rates, a relationship is proposed linking the measured strength properties at low-strain-rates to those controlling the compaction response under dynamic loading. [ABSTRACT FROM AUTHOR]

We present a Nested Markov chain Monte Carlo (NMC) scheme for building equilibrium averages based on accurate potentials such as density functional theory. Metropolis sampling of a reference system, defined by an inexpensive but approximate potential, was used to substantially decorrelate configurations at which the potential of interest was evaluated, thereby dramatically reducing the number needed to build ensemble averages at a given level of precision. The efficiency of this procedure was maximized on-the-fly through variation of the reference system thermodynamic state (characterized here by its inverse temperature β0), which was otherwise unconstrained. Local density approximation results are presented for shocked states of argon at pressures from 4 to 60 GPa, where--depending on the quality of the reference system potential--acceptance probabilities were enhanced by factors of 1.2-28 relative to unoptimized NMC. The optimization procedure compensated strongly for reference potential shortcomings, as evidenced by significantly higher speedups when using a reference potential of lower quality. The efficiency of optimized NMC is shown to be competitive with that of standard ab initio molecular dynamics in the canonical ensemble. [ABSTRACT FROM AUTHOR]

An optimized variant of the nested Markov chain Monte Carlo [n(MC)2] method [J. Chem. Phys. 130, 164104 (2009)] is applied to fluid N2. In this implementation of n(MC)2, isothermal-isobaric (NPT) ensemble sampling on the basis of a pair potential (the “reference” system) is used to enhance the efficiency of sampling based on Perdew–Burke–Ernzerhof density functional theory with a 6-31G* basis set (PBE/6-31G*, the “full” system). A long sequence of Monte Carlo steps taken in the reference system is converted into a trial step taken in the full system; for a good choice of reference potential, these trial steps have a high probability of acceptance. Using decorrelated samples drawn from the reference distribution, the pressure and temperature of the full system are varied such that its distribution overlaps maximally with that of the reference system. Optimized pressures and temperatures then serve as input parameters for n(MC)2 sampling of dense fluid N2 over a wide range of thermodynamic conditions. The simulation results are combined to construct the Hugoniot of nitrogen fluid, yielding predictions in excellent agreement with experiment. [ABSTRACT FROM AUTHOR]

Building on the work of Iftimie et al. [J. Chem. Phys. 113, 4852 (2000)] and Gelb [J. Chem. Phys. 118, 7747 (2003)], Boltzmann sampling of an approximate potential (the “reference” system) is used to build a Markov chain in the isothermal-isobaric ensemble. At the end points of the chain, the energy is evaluated at a more accurate level (the “full” system) and a composite move encompassing all of the intervening steps is accepted on the basis of a modified Metropolis criterion. For reference system chains of sufficient length, consecutive full energies are statistically decorrelated and thus far fewer are required to build ensemble averages with a given variance. Without modifying the original algorithm, however, the maximum reference chain length is too short to decorrelate full configurations without dramatically lowering the acceptance probability of the composite move. This difficulty stems from the fact that the reference and full potentials sample different statistical distributions. By manipulating the thermodynamic variables characterizing the reference system (pressure and temperature, in this case), we maximize the average acceptance probability of composite moves, lengthening significantly the random walk between consecutive full energy evaluations. In this manner, the number of full energy evaluations needed to precisely characterize equilibrium properties is dramatically reduced. The method is applied to a model fluid, but implications for sampling high-dimensional systems with ab initio or density functional theory potentials are discussed. [ABSTRACT FROM AUTHOR]

The full multiple spawning (FMS) method has been developed to simulate quantum dynamics in the multistate electronic problem. In FMS, the nuclear wave function is represented in a basis of coupled, frozen Gaussians, and a “spawning” procedure prescribes a means of adaptively increasing the size of this basis in order to capture population transfer between electronic states. Herein we detail a new algorithm for specifying the initial conditions of newly spawned basis functions that minimizes the number of spawned basis functions needed for convergence. “Optimally” spawned basis functions are placed to maximize the coupling between parent and child trajectories at the point of spawning. The method is tested with a two-state, one-mode avoided crossing model and a two-state, two-mode conical intersection model. [ABSTRACT FROM AUTHOR]

The excited-state dynamics is calculated by using ab initio molecular dynamics with a multireference perturbation theory description of the electronic structure. The results have shown that the lack of an observed effect in the reaction is due to multidimensionality of the reaction coordinate, where heavy-atom bond alteration is involved instead of proton transfer.

The intersections involving a simultaneous degeneracy of two electronic states are highlighted. Molecules exhibiting excited-state intramolecular proton transfer provide a framework for understanding the fundamental phenomenon of photoacidity.