Microscopic calculations of Hugoniot curves of neat triaminotrinitrobenzene (TATB) and of its detonation products.

We compute the Hugoniot curves of both neat triaminotrinitrobenzene (TATB) and its detonation products mixture using atomistic simulation tools. To compute the Hugoniot states, we adapted our sampling constraints in average (SCA) method (Maillet et al. Appl. Math. Res. eXpress 2009, 2008, abn004) to Monte Carlo simulations. For neat TATB, we show that the potential proposed by Rai (Rai et al. J. Chem. Phys. 2008, 129, 194510) is not accurate enough to predict the Hugoniot curve and requires some optimization of its parameters. Concerning the detonation products, thermodynamic properties at chemical equilibrium are computed using a specific reaction ensemble Monte Carlo (RxMC) method (Bourasseau et al. Phys. Chem. Chem. Phys. 2011, 13, 7060), taking into account the presence of carbon clusters in the fluid mixture. We show that this explicit description of the solid phase immersed in the fluid phase modifies the chemical equilibrium.

Bootstrapping time correlation functions of molecular dynamics.

Molecular dynamics is often considered as a numerical experiment. The error bars on the results are therefore mandatory, but sometimes difficult to determine and computationally demanding. As a low-cost approach, we describe the application of the bootstrap (BS) method to the quantification of uncertainties pertaining to the time correlation functions. We chose the autocorrelation functions of velocity and interdiffusion current for a binary ionic mixture as a test bed, and we assessed the merit of the Darken approximation relating both of them. The intrinsic errors related to phase space sampling is investigated comparing the BS method with the reference method of replica. We also study how the BS method can assist in addressing the finite-size effects.

Microscopic approaches to liquid nitromethane detonation properties.

In this paper, thermodynamic and chemical properties of nitromethane are investigated using microscopic simulations. The Hugoniot curve of the inert explosive is computed using Monte Carlo simulations with a modified version of the adaptative Erpenbeck equation of state and a recently developed intermolecular potential. Molecular dynamic simulations of nitromethane decomposition have been performed using a reactive potential, allowing the calculation of kinetic rate constants and activation energies. Finally, the Crussard curve of detonation products as well as thermodynamic properties at the Chapman-Jouguet (CJ) point are computed using reactive ensemble Monte Carlo simulations. Results are in good agreement with both thermochemical calculations and experimental measurements.

Thermodynamic behavior of the CO2 + NO2/N2O4 mixture: a Monte Carlo simulation study.

The thermodynamic behavior of the carbon dioxide + nitrogen dioxide (CO2 + NO2) mixture was investigated using a Monte Carlo molecular simulation approach. This system is a particularly challenging one because nitrogen dioxide exists as a mixture of monomers (NO2) and dimers (N2O4) under certain pressure and temperature conditions. The chemical equilibrium between N2O4 and 2NO2 and the vapor-liquid equilibrium of CO2 + NO2/N2O4 mixtures were simulated using simultaneously the reaction ensemble and the Gibbs ensemble Monte Carlo (RxMC and GEMC) methods. Rigid all atoms molecular potentials bearing point charges were proposed to model both NO2 and N2O4 species. Liquid-vapor coexistence properties of the reacting NO2/N2O4 system were first investigated. The calculated vapor pressures and coexisting densities were compared to experimental values, leading to an average deviation of 10% for vapor pressures and 6% for liquid densities. The critical region was also addressed successfully using the subcritical Monte Carlo simulation results and some appropriate scaling laws. Predictions of CO2 + NO2/N2O4 phase diagrams at 300, 313, and 330 K were then proposed. Derivative properties calculations were also performed in the reaction ensemble at constant pressure and temperature for both NO2/N2O4 and CO2 + NO2/N2O4 systems. The calculated heat capacities show a maximum in the temperature range where N2O4 dissociation occurs, in agreement with available experimental data.

Correlation and transport properties for mixtures at constant pressure and temperature.

Transport properties of mixtures of elements in the dense plasma regime play an important role in natural astrophysical and experimental systems, e.g., inertial confinement fusion. We present a series of orbital-free molecular dynamics simulations on dense plasma mixtures with comparison to a global pseudo ion in jellium model. Hydrogen is mixed with elements of increasingly high atomic number (lithium, carbon, aluminum, copper, and silver) at a fixed temperature of 100 eV and constant pressure set by pure hydrogen at 2g/cm^{3}, namely, 370 Mbars. We compute ionic transport coefficients, such as self-diffusion, mutual diffusion, and viscosity for various concentrations. Small concentrations of the heavy atoms significantly change the density of the plasma and decrease the transport coefficients. The structure of the mixture evidences a strong Coulomb coupling between heavy ions and the appearance of a broad correlation peak at short distances between hydrogen atoms. The concept of an effective one component plasma is used to quantify the overcorrelation of the light element induced by the admixture of a heavy element.

Bayesian inference of x-ray diffraction spectra from warm dense matter with the one-component-plasma model.

We show that the Bayesian inference of recently measured x-ray diffraction spectra from laser-shocked aluminum [L. B. Fletcher et al., Nat. Photon. 9, 274 (2015)10.1038/nphoton.2015.41] with the one-component-plasma (OCP) model performs remarkably well at estimating the ionic density and temperature. This statistical approach requires many evaluations of the OCP static structure factor, which were done using a recently derived analytic fit. The atomic form factor is approximated by an exponential function in the diffraction window of the first peak. The electronic temperature is then estimated from a comparison of this approximated form factor with the electronic structure of an average atom model. Out-of-equilibrium states, with electrons hotter than ions, are diagnosed for the spectra obtained early after the pump, whereas at a late time delay the plasma is at thermal equilibrium. Apart from the present findings, this OCP-based modeling of warm dense matter has an important role to play in the interpretation of x-ray Thomson scattering measurements currently performed at large laser facilities.

Water condensation in hydrophobic silicalite-1 zeolite: a molecular simulation study.

We report grand canonical Monte Carlo simulations of the gas and liquid phase adsorption of water in silicalite-1 zeolite. Simple but effective models and simulation methods, found useful for studying gas adsorption in nanoporous materials, have been extended to describe the intrusion/extrusion cycle of water in this hydrophobic solid. The picture of water confined to hydrophobic spaces of nanoscopic dimensions that emerges from this study is one of a strongly depleted and highly inhomogeneous fluid.

Simple calculation of ab initio melting curves: Application to aluminum.

We present a simple, fast, and promising method to compute the melting curves of materials with ab initio molecular dynamics. It is based on the two-phase thermodynamic model of Lin et al [J. Chem. Phys. 119, 11792 (2003)] and its improved version given by Desjarlais [Phys. Rev. E 88, 062145 (2013)]. In this model, the velocity autocorrelation function is utilized to calculate the contribution of the nuclei motion to the entropy of the solid and liquid phases. It is then possible to find the thermodynamic conditions of equal Gibbs free energy between these phases, defining the melting curve. The first benchmark on the face-centered cubic melting curve of aluminum from 0 to 300 GPa demonstrates how to obtain an accuracy of 5%-10%, comparable to the most sophisticated methods, for a much lower computational cost.

Molecular based equation of state for shocked liquid nitromethane.

An approach is proposed to obtain the equation of state of unreactive shocked liquid nitromethane. Unlike previous major works, this equation of state is not based on extended integration schemes [P.C. Lysne, D.R. Hardesty, Fundamental equation of state of liquid nitromethane to 100 kbar, J. Chem. Phys. 59 (1973) 6512]. It does not follow the way proposed by Winey et al. [J.M. Winey, G.E. Duvall, M.D. Knudson, Y.M. Gupta, Equation of state and temperature measurements for shocked nitromethane, J. Chem. Phys. 113 (2000) 7492] where the specific heat C(v), the isothermal bulk modulus B(T) and the coefficient of thermal pressure (deltaP/deltaT)(v) are modeled as functions of temperature and volume using experimental data. In this work, we compute the complete equation of state by microscopic calculations. Indeed, by means of Monte Carlo molecular simulations, we have proposed a new force field for nitromethane that lead to a good description of shock properties [N. Desbiens, E. Bourasseau, J.-B. Maillet, Potential optimization for the calculation of shocked liquid nitromethane properties, Mol. Sim. 33 (2007) 1061; A. Hervouët, N. Desbiens, E. Bourasseau, J.-B. Maillet, Microscopic approaches to liquid nitromethane detonation properties, J. Phys. Chem. B 112 (2008) 5070]. Particularly, it has been shown that shock temperatures and second shock temperatures are accurately reproduced which is significative of the quality of the potential. Here, thermodynamic derivative properties are computed: specific heats, Grüneisen parameter, sound velocity among others, along the Hugoniot curve. This work constitutes to our knowledge the first determination of the equation of state of an unreactive shocked explosive by molecular simulations.

Molecular simulations of Hugoniots of detonation product mixtures at chemical equilibrium: microscopic calculation of the Chapman-Jouguet state.

In this work, we used simultaneously the reaction ensemble Monte Carlo (ReMC) method and the adaptive Erpenbeck equation of state (AE-EOS) method to directly calculate the thermodynamic and chemical equilibria of mixtures of detonation products on the Hugoniot curve. The ReMC method [W. R. Smith and B. Triska, J. Chem. Phys. 100, 3019 (1994)] allows us to reach the chemical equilibrium of a reacting mixture, and the AE-EOS method [J. J. Erpenbeck, Phys. Rev. A 46, 6406 (1992)] constrains the system to satisfy the Hugoniot relation. Once the Hugoniot curve of the detonation product mixture is established, the Chapman-Jouguet (CJ) state of the explosive can be determined. A NPT simulation at P(CJ) and T(CJ) is then performed in order to calculate direct thermodynamic properties and the following derivative properties of the system using a fluctuation method: calorific capacities, sound velocity, and Gruneisen coefficient. As the chemical composition fluctuates, and the number of particles is not necessarily constant in this ensemble, a fluctuation formula has been developed to take into account the fluctuations of mole number and composition. This type of calculation has been applied to several usual energetic materials: nitromethane, tetranitromethane, hexanitroethane, PETN, and RDX.

Molecular simulation studies of water physisorption in zeolites.

We report a series of Grand Canonical Monte Carlo simulations of water adsorption in NaY and NaX faujasite, as well as in silicalite-1. Computed adsorption isotherms and heats of adsorption were in good agreement with the available experiments. The existence of cyclic water hexamers in NaX located in the 12-ring windows, recently disclosed by neutron diffraction experiments (Hunger et al., J. Phys. Chem. B, 2006, 110, 342-353) was reproduced in our simulations. Interestingly enough, such cyclic hexamer clusters were also observed in the case of NaY, in which no stabilizing cation is present in the 12-ring window. We also report cation redistribution upon water adsorption for sodium faujasite with varying cation contents (Si ratio Al ratio in the range 1.53-3). A simple and transferable forcefield was used, that enabled to reproduce the different aspects of water physisorption in stable zeolites. The high pressure water condensation in hydrophobic silicalite-1 was reproduced without any parameter readjustment. The method and forcefield used here should be useful for engineering oriented applications such as the prediction of multi-component mixture adsorptive separations in various stable zeolites. It allows to address the issue of the effect of the small amounts of water that are almost inevitably present in zeolite-based separation processes.