Evidence for Dissociation and Ionization in Shock Compressed Nitrogen to 800 GPa.

Triple bonding in the nitrogen molecule (N_{2}) is among the strongest chemical bonds with a dissociation enthalpy of 9.8 eV/molecule. Nitrogen is therefore an excellent test bed for theoretical and numerical methods aimed at understanding how bonding evolves under the influence of the extreme pressures and temperatures of the warm dense matter regime. Here, we report laser-driven shock experiments on fluid molecular nitrogen up to 800 GPa and 4.0 g/cm^{3}. Line-imaging velocimetry measurements and impedance matching method with a quartz reference yield shock equation of state data of initially precompressed nitrogen. Comparison with numerical simulations using path integral Monte Carlo and density functional theory molecular dynamics reveals clear signatures of chemical dissociation and the onset of L-shell ionization. Combining data along multiple shock Hugoniot curves starting from densities between 0.76 and 1.29 g/cm^{3}, our study documents how pressure and density affect these changes in chemical bonding and provides benchmarks for future theoretical developments in this regime, with applications for planetary interior modeling, high energy density science, and inertial confinement fusion research.

Magnesium oxide at extreme temperatures and pressures studied with first-principles simulations.

We combine two first-principles computer simulation techniques, path integral Monte Carlo and density functional theory molecular dynamics, to determine the equation of state of magnesium oxide in the regime of warm dense matter, with densities ranging from 0.35 to 71 g cm-3 and temperatures ranging from 10 000 K to 5 × 108 K. These conditions are relevant for the interiors of giant planets and stars as well as for shock wave compression measurements and inertial confinement fusion experiments. We study the electronic structure of MgO and the ionization mechanisms as a function of density and temperature. We show that the L-shell orbitals of magnesium and oxygen hybridize at high density. This results in a gradual ionization of the L-shell with increasing density and temperature. In this regard, MgO behaves differently from pure oxygen, which is reflected in the shape of the MgO principal shock Hugoniot curve. The curve of oxygen shows two compression maxima, while that of MgO shows only one. We predict a maximum compression ratio of 4.66 to occur for a temperature of 6.73 × 107 K. Finally, we study how multiple shocks and ramp waves can be used to cover a large range of densities and temperatures.

Path integral Monte Carlo simulations of dense carbon-hydrogen plasmas.

Carbon-hydrogen plasmas and hydrocarbon materials are of broad interest to laser shock experimentalists, high energy density physicists, and astrophysicists. Accurate equations of state (EOSs) of hydrocarbons are valuable for various studies from inertial confinement fusion to planetary science. By combining path integral Monte Carlo (PIMC) results at high temperatures and density functional theory molecular dynamics results at lower temperatures, we compute the EOSs for hydrocarbons from simulations performed at 1473 separate (ρ, T)-points distributed over a range of compositions. These methods accurately treat electronic excitation effects with neither adjustable parameter nor experimental input. PIMC is also an accurate simulation method that is capable of treating many-body interaction and nuclear quantum effects at finite temperatures. These methods therefore provide a benchmark-quality EOS that surpasses that of semi-empirical and Thomas-Fermi-based methods in the warm dense matter regime. By comparing our first-principles EOS to the LEOS 5112 model for CH, we validate the specific heat assumptions in this model but suggest that the Grüneisen parameter is too large at low temperatures. Based on our first-principles EOSs, we predict the principal Hugoniot curve of polystyrene to be 2%-5% softer at maximum shock compression than that predicted by orbital-free density functional theory and SESAME 7593. By investigating the atomic structure and chemical bonding of hydrocarbons, we show a drastic decrease in the lifetime of chemical bonds in the pressure interval from 0.4 to 4 megabar. We find the assumption of linear mixing to be valid for describing the EOS and the shock Hugoniot curve of hydrocarbons in the regime of partially ionized atomic liquids. We make predictions of the shock compression of glow-discharge polymers and investigate the effects of oxygen content and C:H ratio on its Hugoniot curve. Our full suite of first-principles simulation results may be used to benchmark future theoretical investigations pertaining to hydrocarbon EOSs and should be helpful in guiding the design of future experiments on hydrocarbons in the gigabar regime.

Equation of state and shock compression of warm dense sodium-A first-principles study.

As one of the simple alkali metals, sodium has been of fundamental interest for shock physics experiments, but knowledge of its equation of state (EOS) in hot, dense regimes is not well known. By combining path integral Monte Carlo (PIMC) results for partially ionized states [B. Militzer and K. P. Driver, Phys. Rev. Lett. 115, 176403 (2015)] at high temperatures and density functional theory molecular dynamics (DFT-MD) results at lower temperatures, we have constructed a coherent equation of state for sodium over a wide density-temperature range of 1.93-11.60 g/cm3 and 103-1.29×108 K. We find that a localized, Hartree-Fock nodal structure in PIMC yields pressures and internal energies that are consistent with DFT-MD at intermediate temperatures of 2×106 K. Since PIMC and DFT-MD provide a first-principles treatment of electron shell and excitation effects, we are able to identify two compression maxima in the shock Hugoniot curve corresponding to K-shell and L-shell ionization. Our Hugoniot curves provide a benchmark for widely used EOS models: SESAME, LEOS, and Purgatorio. Due to the low ambient density, sodium has an unusually high first compression maximum along the shock Hugoniot curve. At beyond 107 K, we show that the radiation effect leads to very high compression along the Hugoniot curve, surpassing relativistic corrections, and observe an increasing deviation of the shock and particle velocities from a linear relation. We also compute the temperature-density dependence of thermal and pressure ionization processes.

Development of Path Integral Monte Carlo Simulations with Localized Nodal Surfaces for Second-Row Elements.

We extend the applicability range of fermionic path integral Monte Carlo simulations to heavier elements and lower temperatures by introducing various localized nodal surfaces. Hartree-Fock nodes yield the most accurate prediction for pressure and internal energy, which we combine with the results from density functional molecular dynamics simulations to obtain a consistent equation of state for hot, dense silicon under plasma conditions and in the regime of warm dense matter (2.3-18.6 g cm(-3), 5.0×10(5)-1.3×10(8) K). The shock Hugoniot curve is derived and the structure of the fluid is characterized with various pair correlation functions.

First-principles equation of state database for warm dense matter computation.

We put together a first-principles equation of state (FPEOS) database for matter at extreme conditions by combining results from path integral Monte Carlo and density functional molecular dynamics simulations of the elements H, He, B, C, N, O, Ne, Na, Mg, Al, and Si as well as the compounds LiF, B_{4}C, BN, CH_{4}, CH_{2}, C_{2}H_{3}, CH, C_{2}H, MgO, and MgSiO_{3}. For all these materials, we provide the pressure and internal energy over a density-temperature range from ∼0.5 to 50 g cm^{-3} and from ∼10^{4} to 10^{9} K, which are based on ∼5000 different first-principles simulations. We compute isobars, adiabats, and shock Hugoniot curves in the regime of L- and K-shell ionization. Invoking the linear mixing approximation, we study the properties of mixtures at high density and temperature. We derive the Hugoniot curves for water and alumina as well as for carbon-oxygen, helium-neon, and CH-silicon mixtures. We predict the maximal shock compression ratios of H_{2}O, H_{2}O_{2}, Al_{2}O_{3}, CO, and CO_{2} to be 4.61, 4.64, 4.64, 4.89, and 4.83, respectively. Finally we use the FPEOS database to determine the points of maximum shock compression for all available binary mixtures. We identify mixtures that reach higher shock compression ratios than their end members. We discuss trends common to all mixtures in pressure-temperature and particle-shock velocity spaces. In the Supplemental Material, we provide all FPEOS tables as well as computer codes for interpolation, Hugoniot calculations, and plots of various thermodynamic functions.

First-principles equation of state and shock compression predictions of warm dense hydrocarbons.

We use path integral Monte Carlo and density functional molecular dynamics to construct a coherent set of equations of state (EOS) for a series of hydrocarbon materials with various C:H ratios (2:1, 1:1, 2:3, 1:2, and 1:4) over the range of 0.07-22.4gcm^{-3} and 6.7×10^{3}-1.29×10^{8}K. The shock Hugoniot curve derived for each material displays a single compression maximum corresponding to K-shell ionization. For C:H = 1:1, the compression maximum occurs at 4.7-fold of the initial density and we show radiation effects significantly increase the shock compression ratio above 2 Gbar, surpassing relativistic effects. The single-peaked structure of the Hugoniot curves contrasts with previous work on higher-Z plasmas, which exhibit a two-peak structure corresponding to both K- and L-shell ionization. Analysis of the electronic density of states reveals that the change in Hugoniot structure is due to merging of the L-shell eigenstates in carbon, while they remain distinct for higher-Z elements. Finally, we show that the isobaric-isothermal linear mixing rule for carbon and hydrogen EOS is a reasonable approximation with errors better than 1% for stellar-core conditions.