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Metallic hydrogen is expected to exhibit remarkable physics. Of particular interest in this work is the possibility of high-temperature superconductivity. Comparing calculations of the superconducting critical temperatures of the solid phase to melting temperatures over a range of pressures leads to an interesting question: Will the solid, in a superconducting state, melt to a liquid that remains a superconductor? In this work, the possibility of liquid superconductivity in metallic hydrogen is investigated. This is done by first-principles simulations, and using the results of these to solve the Eliashberg equations. These are carried out over the pressure (and temperature) conditions where molecular dissociation is expected to first occur in the solid phase. Over the pressure range $386.8(4)$--$783.7(4)$ GPa, $T_c$ increases from $308(6)$ to $372(2)$ K with a maximum uncertainty of $10$ K; it then decreases to $356(2)$ K at $883.7(3)$ GPa. Comparisons to the solid phase show that the critical temperature is not significantly changed between the two phases, though the physics behind their superconductivity is different. Careful comparisons of these values to recent results in the context of the hydrogen phase diagram show that they are higher than the melting temperatures and that the solid will melt to liquid atomic hydrogen. The results of this work (in this context) therefore suggest that liquid atomic hydrogen will indeed exist in a superconducting state. They also provide the pressure and temperature conditions over which to look for it.

Metallic hydrogen is expected to exhibit remarkable physics. However, the pressures at which it is expected to be stable are extremely high relative to current experimental capabilities (static conditions). For practical (and terrestrial) significance, a key question is therefore whether it is metastable. In this work, this possibility is investigated, using first-principles calculations. Particular attention is given to the atomic body-centered tetragonal structures, predicted as being representative of the lowest-pressure stable metallic phase. The results show that, of these, the Cs-IV structure is metastable upon decompression, from molecular dissociation (expected to occur just below 500 GPa) to approximately 250 GPa. Results for structure prediction for metallic phases at lower pressures are also presented. Together, these results suggest that below 200 GPa, metallic hydrogen has no region of stability. All of the approximations used in the calculations are considered, and they are not expected to qualitatively affect the results. Atomic metallic hydrogen is therefore expected to have a (pressure) region of metastability, but the results strongly suggest that the metallic phase (more generally) is not so to zero pressure. These results are expected to provide important information for experiments.

A fluid flow in a nanochannel highly depends on the wettability of the channel surface to the fluid. The permeability of the nanochannel is usually very low, largely due to the adhesion of fluid at the solid interfaces. Using molecular dynamics (MD) simulations, we demonstrate that the flow of water in a nanochannel with rough hydrophilic surfaces can be significantly enhanced by the presence of a thin layer of supercritical carbon dioxide (scCO2) at the water-solid interfaces. The thin scCO2 layer acts like an atomistic lubricant that transforms a hydrophilic interface into a super-hydrophobic one and triggers a transition from a stick- to- a slip boundary condition for a nanoscale flow. This work provides an atomistic insight into multicomponent interactions in nanochannels and illustrates that such interactions can be manipulated, if needed, to increase the throughput and energy efficiency of nanofluidic systems.

Capture and subsequent geologic storage of CO2 in deep brine reservoirs plays a significant role in plans to reduce atmospheric carbon emission and resulting global climate change. Subsurface injection of CO2 is also used industrially in enhanced oil and natural gas recovery operations to increase the amount of hydrocarbon that can be economically recovered from a geologic reservoir. The interaction of CO2 and brine species with mineral surfaces controls the ultimate fate of injected CO2 at the nanoscale via surface chemistry, at the pore-scale via capillary trapping, and at the field-scale via relative permeability. High resolution micro X-ray CT scanning, optical contact angle measurements, and large scale molecular dynamics simulations were used to investigate the behavior of supercritical CO2 and aqueous fluids on basal surfaces of muscovite, a common phyllosilicate mineral. Experimental results demonstrate partial wetting by the aqueous phase and a dependence of contact angle upon aqueous phase brine composition. This contrasts with simulation results, which predict that supercritical CO2 forms a non-wetting droplet, separated from direct interaction with the muscovite surface by distinct layers of water and charged species. Simulations with trace amounts of acetate or acetic acid added to the CO2/water/mineral system were used to investigate the potential effect of contamination with small organic molecules. While the observed contact angle was not significantly altered, these simulations demonstrate the influence of pH on species partitioning, with acetic acid molecules partitioning to the CO2/water interface and acetate ions adsorbing to the mineral surface. Similar simulations using hexanoate displayed a greater surfactant effect and significantly increased wetting by the CO2 phase, suggesting that small concentrations of secondary species or contaminants can significantly influence macroscopic wetting behavior.

First-principles molecular dynamics simulations were used to investigate the dissociation of sarin (GB) on the calcium silicate hydrate (CSH) mineral tobermorite (TBM), a surrogate for cement. CSH minerals (including TBM) and amorphous materials of similar composition are the major components of Portland cement, the binding agent of concrete. Metadynamics simulations were used to investigate the effect of the TBM surface and confinement in a microscale pore on the mechanism and free energy of dissociation of GB. Our results indicate that both the adsorption site and the humidity of the local environment significantly affect the sarin dissociation energy. In particular, sarin dissociation in a low-water environment occurs via a dealkylation mechanism, which is consistent with previous experimental studies.

A fluid flow in a nanochannel highly depends on the wettability of the channel surface to the fluid. The permeability of the nanochannel is usually very low, largely due to the adhesion of fluid at the solid interfaces. Using molecular dynamics (MD) simulations, we demonstrate that the flow of water in a nanochannel with rough hydrophilic surfaces can be significantly enhanced by the presence of a thin layer of supercritical carbon dioxide (scCO2) at the water-solid interfaces. The thin scCO2 layer acts like an atomistic lubricant that transforms a hydrophilic interface into a super-hydrophobic one and triggers a transition from a stick- to- a slip boundary condition for a nanoscale flow. This work provides an atomistic insight into multicomponent interactions in nanochannels and illustrates that such interactions can be manipulated, if needed, to increase the throughput and energy efficiency of nanofluidic systems.

Geological storage of CO2 (GCS), also referred to as carbon sequestration, is a critical component for decreasing anthropogenic CO2 atmospheric emissions. Stored CO2 will exist as a supercritical phase, most likely in deep, saline, sedimentary reservoirs. Research at the Center for Frontiers of Subsurface Energy Security (CFSES), a Department of Energy, Energy Frontier Research Center, provides insights into the storage process. The integration of pore-scale experiments, molecular dynamics simulations, and study of natural analogue sites has enabled understanding of the efficacy of capillary, solubility, and dissolution trapping of CO2 for GCS. Molecular dynamics simulations provide insight on relative wetting of supercritical CO2 and brine hydrophilic and hydrophobic basal surfaces of kaolinite. Column experiments of successive supercritical CO2/brine flooding with high-resolution X-ray computed tomography imaging show a greater than 10% difference of residual trapping of CO2 in hydrophobic media compare...

Graph theoretic tools were used to identify and classify clusters of ions and solvent molecules in molecular dynamics simulations of lithium-ion battery electrolytes. Electrolytes composed of various concentrations of LiPF6 dissolved in ethylene carbonate (EC), dimethylene carbonate (DMC), or a 1:1 EC/DMC mixture were simulated at multiple temperatures using classical molecular dynamics. Contrary to Nernst–Einstein theory but consistent with experiment, pure DMC systems had the greatest diffusivity but the lowest conductivity. This disagreement with Nernst–Einstein theory is explained by the observed clustering behavior, which found that systems with pure EC as a solvent formed ion clusters with nonzero charge, whereas systems with pure DMC as a solvent formed primarily neutral clusters.

Results of molecular dynamics simulations are reported in which the structure and dynamics of the reacted and unreacted forms of the task-specific ionic liquid (TSIL) tetrabutylphosphonium 2-cyanopyrrolide were computed. This particular ionic liquid is one of several newly discovered TSILs containing aprotic heterocyclic anions designed specifically for CO2 capture. The physical properties, liquid structure, and dynamics of the ionic liquid were computed as a function of extent of reaction with CO2. Translational and rotational dynamics showed little change upon reaction with CO2, in sharp contrast to traditional TSILs and consistent with experimental viscosity measurements. It is shown that this is due to the failure of a hydrogen-bond network to form upon reaction with CO2. The Henry’s law constants for the physical solubility of CO2, N2, O2, and H2O were computed for the unreacted TSIL and found to be comparable to values observed with other ionic liquids. In the reacted state, the solubility of CO2, N...

The current expansion of natural gas (NG) development in the United States requires an understanding of how this change will affect the natural gas industry, downstream consumers, and economic growth in order to promote effective planning and policy development. The impact of this expansion may propagate through the NG system and US economy via changes in manufacturing, electric power generation, transportation, commerce, and increased exports of liquefied natural gas. We conceptualize this problem as supply shock propagation that pushes the NG system and the economy away from its current state of infrastructure development and level of natural gas use. To illustrate this, the project developed two core modeling approaches. The first is an Agent-Based Modeling (ABM) approach which addresses shock propagation throughout the existing natural gas distribution system. The second approach uses a System Dynamics-based model to illustrate the feedback mechanisms related to finding new supplies of natural gas - notably shale gas - and how those mechanisms affect exploration investments in the natural gas market with respect to proven reserves. The ABM illustrates several stylized scenarios of large liquefied natural gas (LNG) exports from the U.S. The ABM preliminary results demonstrate that such scenario is likely to have substantialmore » effects on NG prices and on pipeline capacity utilization. Our preliminary results indicate that the price of natural gas in the U.S. may rise by about 50% when the LNG exports represent 15% of the system-wide demand. The main findings of the System Dynamics model indicate that proven reserves for coalbed methane, conventional gas and now shale gas can be adequately modeled based on a combination of geologic, economic and technology-based variables. A base case scenario matches historical proven reserves data for these three types of natural gas. An environmental scenario, based on implementing a $50/tonne CO 2 tax results in less proven reserves being developed in the coming years while demand may decrease in the absence of acceptable substitutes, incentives or changes in consumer behavior. An increase in demand of 25% increases proven reserves being developed by a very small amount by the end of the forecast period of 2025.« less

Capture and subsequent geologic storage of CO2 in deep brine reservoirs plays a significant role in plans to reduce atmospheric carbon emission and resulting global climate change. The interaction of CO2 and brine species with mineral surfaces controls the ultimate fate of injected CO2 at the nanoscale via geochemistry, at the pore-scale via capillary trapping, and at the field-scale via relative permeability. We used large-scale molecular dynamics simulations to study the behavior of supercritical CO2 and aqueous fluids on both the hydrophilic and hydrophobic basal surfaces of kaolinite, a common clay mineral. In the presence of a bulk aqueous phase, supercritical CO2 forms a nonwetting droplet above the hydrophilic surface of kaolinite. This CO2 droplet is separated from the mineral surface by distinct layers of water, which prevent the CO2 droplet from interacting directly with the mineral surface. Conversely, both CO2 and H2O molecules interact directly with the hydrophobic surface of kaolinite. In the presence of bulk supercritical CO2, nonwetting aqueous droplets interact with the hydrophobic surface of kaolinite via a mixture of adsorbed CO2 and H2O molecules. Because nucleation and precipitation of minerals should depend strongly on the local distribution of CO2, H2O, and ion species, these nanoscale surface interactions are expected to influence long-term mineralization of injected carbon dioxide.

In lithium ion batteries, Li+ intercalation and processes associated with passivation of electrodes are governed by applied voltages, which are in turn associated with free energy changes of Li+ transfer (Delta G_t) between the solid and liquid phases. Using ab initio molecular dynamics (AIMD) and thermodynamic integration techniques, we compute Delta G_t for the virtual transfer of a Li+ from a LiC(6) anode slab, with pristine basal planes exposed, to liquid ethylene carbonate confined in a nanogap. The onset of delithiation, at Delta G_t=0, is found to occur on LiC(6) anodes with negatively charged basal surfaces. These negative surface charges are evidently needed to retain Li+ inside the electrode, and should affect passivation ("SEI") film formation processes. Fast electrolyte decomposition is observed at even larger electron surface densities. By assigning the experimentally known voltage (0.1 V vs. Li+/Li metal) to the predicted delithiation onset, an absolute potential scale is obtained. This enables voltage calibrations in simulation cells used in AIMD studies, and paves the way for future prediction of voltage dependences in interfacial processes in batteries., 8 figures

Reprocessing of the Parkes Multibeam Pulsar Survey has resulted in the discovery of five previously unknown pulsars and several as-yet-unconfirmed candidates. PSR J0922-52 has a period of 9.68 ms and a DM of 122.4 pc cm^-3. PSR J1147-66 has a period of 3.72 ms and a DM of 133.8 pc cm^-3. PSR J1227-6208 has a period of 34.53 ms, a DM of 362.6 pc cm^-3, is in a 6.7 day binary orbit, and was independently detected in an ongoing high-resolution Parkes survey by Thornton et al. and also in independent processing by Einstein@Home volunteers. PSR J1546-59 has a period of 7.80 ms and a DM of 168.3 pc cm^-3. PSR J1725-3853 is an isolated 4.79-ms pulsar with a DM of 158.2 pc cm^-3. These pulsars were likely missed in earlier processing efforts due to their high DMs and short periods and the large number of candidates that needed to be looked through. These discoveries suggest that further pulsars are awaiting discovery in the multibeam survey data., Comment: 12 pages, 2 figures, 2 tables, accepted to ApJ

The reverse nonequilibrium molecular dynamics (RNEMD) method calculates the shear viscosity of a fluid by imposing a nonphysical exchange of momentum and measuring the resulting shear velocity gradient. In this study we investigate the range of momentum flux values over which RNEMD yields usable (linear) velocity gradients. We find that nonlinear velocity profiles result primarily from gradients in fluid temperature and density. The temperature gradient results from conversion of heat into bulk kinetic energy, which is transformed back into heat elsewhere via viscous heating. An expression is derived to predict the temperature profile resulting from a specified momentum flux for a given fluid and simulation cell. Although primarily bounded above, we also describe milder low-flux limitations. RNEMD results for a Lennard-Jones fluid agree with equilibrium molecular dynamics and conventional nonequilibrium molecular dynamics calculations at low shear, but RNEMD underpredicts viscosity relative to conventional NEMD at high shear.