Thomas-Fermi-Dirac-von Weizsacker hydrodynamics in laterally modulated electronic systems

We have studied the collective plasma excitations of a two-dimensional electron gas with an arbitrary lateral charge-density modulation. The dynamics is formulated using a previously developed hydrodynamic theory based on the Thomas-Fermi-Dirac-von Weizsacker approximation. In this approach, both the equilibrium and dynamical properties of the periodically modulated electron gas are treated in a consistent fashion. We pay particular attention to the evolution of the collective excitations as the system undergoes the transition from the ideal two-dimensional limit to the highly-localized one-dimensional limit. We also calculate the power absorption in the long-wavelength limit to illustrate the effect of the modulation on the modes probed by far-infrared (FIR) transmission spectroscopy.Comment: 27 page Revtex file, 15 Postscript figure

Prewetting transitions of Ar and Ne on alkali metal surfaces

We have studied by means of Density-Functional calculations the wetting properties of Ar and Ne adsorbed on a plane whose adsorption properties simulate the Li and Na surfaces. We use reliable ab-initio potentials to model the gas-substrate interactions. Evidence for prewetting transitions is found for all the systems investigated and their wetting phase diagrams are calculated.Comment: 6 pages, 8 figures, submitted for publication in Phys. Rev.

Wetting transitions of Ne

We report studies of the wetting behavior of Ne on very weakly attractive surfaces, carried out with the Grand Canonical Monte Carlo method. The Ne-Ne interaction was taken to be of Lennard-Jones form, while the Ne-surface interaction was derived from an ab initio calculation of Chizmeshya et al. Nonwetting behavior was found for Li, Rb, and Cs in the temperature regime explored (i.e., T < 42 K). Drying behavior was manifested in a depleted fluid density near the Cs surface. In contrast, for the case of Mg (a more attractive potential) a prewetting transition was found near T= 28 K. This temperature was found to shift slightly when a corrugated potential was used instead of a uniform potential. The isotherm shape and the density profiles did not differ qualitatively between these cases.Comment: 22 pages, 12 figures, submitted to Phys. Rev.

To wet or not to wet: that is the question

Wetting transitions have been predicted and observed to occur for various combinations of fluids and surfaces. This paper describes the origin of such transitions, for liquid films on solid surfaces, in terms of the gas-surface interaction potentials V(r), which depend on the specific adsorption system. The transitions of light inert gases and H2 molecules on alkali metal surfaces have been explored extensively and are relatively well understood in terms of the least attractive adsorption interactions in nature. Much less thoroughly investigated are wetting transitions of Hg, water, heavy inert gases and other molecular films. The basic idea is that nonwetting occurs, for energetic reasons, if the adsorption potential's well-depth D is smaller than, or comparable to, the well-depth of the adsorbate-adsorbate mutual interaction. At the wetting temperature, Tw, the transition to wetting occurs, for entropic reasons, when the liquid's surface tension is sufficiently small that the free energy cost in forming a thick film is sufficiently compensated by the fluid- surface interaction energy. Guidelines useful for exploring wetting transitions of other systems are analyzed, in terms of generic criteria involving the "simple model", which yields results in terms of gas-surface interaction parameters and thermodynamic properties of the bulk adsorbate.Comment: Article accepted for publication in J. Low Temp. Phy

Toward a Density Functional Description of Liquid pH(2)

A finite-temperature density functional approach to describe the properties of parahydrogen in the liquid-vapor coexistence region is presented. The first proposed functional is zero-range, where the density-gradient term is adjusted so as to reproduce the surface tension of the liquid-vapor interface at low temperature. The second functional is finite-range and, while it is fitted to reproduce bulk pH(2) properties only, it is shown to yield surface properties in good agreement with experiments. These functionals are used to study the surface thickness of the liquid-vapor interface, the wetting transition of parahydrogen on a planar Rb model surface, and homogeneous cavitation in bulk liquid pH(2)

Enhancing the Atomic-Level Understanding of co2 Mineral Sequestration Mechanisms via Advanced Computational Modeling

Fossil fuels currently provide 85% of the world's energy needs, with the majority coming from coal, due to its low cost, wide availability, and high energy content. The extensive use of coalfired power assumes that the resulting CO{sub 2} emissions can be vented to the atmosphere. However, exponentially increasing atmospheric CO{sub 2} levels have brought this assumption under critical review. Over the last decade, this discussion has evolved from whether exponentially increasing anthropogenic CO{sub 2} emissions will adversely affect the global environment, to the timing and magnitude of their impact. A variety of sequestration technologies are being explored to mitigate CO{sub 2} emissions. These technologies must be both environmentally benign and economically viable. Mineral carbonation is an attractive candidate technology as it disposes of CO{sub 2} as geologically stable, environmentally benign mineral carbonates, clearly satisfying the first criteria. The primary challenge for mineral carbonation is cost-competitive process development. CO{sub 2} mineral sequestration--the conversion of stationary-source CO{sub 2} emissions into mineral carbonates (e.g., magnesium and calcium carbonate, MgCO{sub 3} and CaCO{sub 3})--has recently emerged as one of the most promising sequestration options, providing permanent CO{sub 2} disposal, rather than storage. In this approach a magnesium-bearing feedstock mineral (typically serpentine or olivine; available in vast quantities globally) is specially processed and allowed to react with CO{sub 2} under controlled conditions. This produces a mineral carbonate which (i) is environmentally benign, (ii) already exists in nature in quantities far exceeding those that could result from carbonating the world's known fossil fuel reserves, and (iii) is stable on a geological time scale. Minimizing the process cost via optimization of the reaction rate and degree of completion is the remaining challenge. As members of the DOE/NETL managed National Mineral Sequestration Working Group we have already significantly improved our understanding of mineral carbonation. Group members at the Albany Research Center have recently shown that carbonation of olivine and serpentine, which naturally occurs over geological time (i.e., 100,000s of years), can be accelerated to near completion in hours. Further process refinement will require a synergetic science/engineering approach that emphasizes simultaneous investigation of both thermodynamic processes and the detailed microscopic, atomic-level mechanisms that govern carbonation kinetics. Our previously funded Phase I Innovative Concepts project demonstrated the value of advanced quantum-mechanical modeling as a complementary tool in bridging important gaps in our understanding of the atomic/molecular structure and reaction mechanisms that govern CO{sub 2} mineral sequestration reaction processes for the model Mg-rich lamellar hydroxide feedstock material Mg(OH){sub 2}. In the present simulation project, improved techniques and more efficient computational schemes have allowed us to expand and augment these capabilities and explore more complex Mg-rich, lamellar hydroxide-based feedstock materials, including the serpentine-based minerals. These feedstock materials are being actively investigated due to their wide availability, and low-cost CO{sub 2} mineral sequestration potential. Cutting-edge first principles quantum chemical, computational solid-state and materials simulation methodology studies proposed herein, have been strategically integrated with our new DOE supported (ASU-Argonne National Laboratory) project to investigate the mechanisms that govern mineral feedstock heat-treatment and aqueous/fluid-phase serpentine mineral carbonation in situ. This unified, synergetic theoretical and experimental approach will provide a deeper understanding of the key reaction mechanisms than either individual approach can alone. Ab initio techniques will also significantly advance our understanding of atomic-level processes at the solid/solution interface by elucidating the origin of vibrational, electronic, x-ray and electron energy loss spectra observed experimentally

Sufficiency conditions for quantum reflection

The mathematics of low-energy scattering from asymptotic power law potentials are examined to extract characteristic lengths of the scattering problem in the limit of low velocity. These are then used to characterize the limiting behavior of the scattering wave function, leading immediately to general, explicit, sufficiency conditions for quantum reflection for arbitrary gas and surface species

Understanding Olivine CO2 Mineral Sequestration Mechanisms at the Atomic Level: Optimizing Reaction Process Design

Carbonation of Mg-rich minerals offers an intriguing candidate carbon sequestration process technology, which can provide large-scale CO{sub 2} disposal. Such disposal bypasses many long-term storage problems by (i) providing containment in the form of mineral carbonates that have proven stable over geological time, (ii) generating only environmentally benign materials, and (iii) essentially eliminating the need for continuous site monitoring. The primary challenge for viable process development is reducing process cost. This is the primary focus of the CO{sub 2} Mineral Sequestration Working Group managed by Fossil Energy at DOE, which includes members from the Albany Research Center, Los Alamos National Laboratory, the National Energy Technology Laboratory, Penn State University, Science Applications International Corporation, and the University of Utah, as well as from our research group at Arizona State University. Carbonation of the widely occurring mineral olivine (e.g., forsterite, Mg{sub 2}SiO{sub 4}) is a leading process candidate, which converts CO{sub 2} into the mineral magnesite (MgCO{sub 3}). As olivine carbonation is exothermic, it offers intriguing low-cost potential. Recent studies at the Albany Research Center have found aqueous-solution carbonation is a promising approach. Cost effectively enhancing carbonation reactivity is central to reducing process cost. Many of the mechanisms that impact reactivity occur at the solid/solution interface. Understanding these mechanisms is central to the ability to engineer new and modified processes to enhance carbonation reactivity and lower cost. Herein, we report the results of our UCR I project, which focused on exploring the reaction mechanisms that govern aqueous-solution olivine carbonation using model olivine feedstock materials. Carbonation was found to be a complex process associated with passivating silica layer formation, which includes the trapping of magnesite nanocrystals within the passivating silica layers, cracking and exfoliation of the layers, silica surface migration, olivine etch pit formation, transfer of the Mg and Fe in the olivine into the product carbonate, and the nucleation and growth of magnesite crystals on/in the silica/olivine reaction matrix. These phenomena occur in concert with the large solid volume changes that accompany the carbonation process, which can substantially impact carbonation reactivity. Passivating silica layer formation appears to play a major role in inhibiting carbonation reactivity. New approaches that can mitigate the effectiveness of passivating layer formation may offer intriguing potential to enhance carbonation reactivity and lower process cost

Simultaneous Mechanical and Heat Activation: A New Route to Enhance Serpentine Carbonation Reactivity and Lower CO2 Mineral Sequestration Process Cost

Coal can support a large fraction of global energy demands for centuries to come, if the environmental problems associated with CO{sub 2} emissions can be overcome. Unlike other candidate technologies, which propose long-term storage (e.g., ocean and geological sequestration), mineral sequestration permanently disposes of CO{sub 2} as geologically stable mineral carbonates. Only benign, naturally occurring materials are formed, eliminating long-term storage and liability issues. Serpentine carbonation is a leading mineral sequestration process candidate, which offers large scale, permanent sequestration. Deposits exceed those needed to carbonate all the CO{sub 2} that could be generated from global coal reserves, and mining and milling costs are reasonable ({approx}$4 to$5/ton). Carbonation is exothermic, providing exciting low-cost process potential. The remaining goal is to develop an economically viable process. An essential step in this development is increasing the carbonation reaction rate and degree of completion, without substantially impacting other process costs. Recently, the Albany Research Center (ARC) has accelerated serpentine carbonation, which occurs naturally over geological time, to near completion in less than an hour. While reaction rates for natural serpentine have been found to be too slow for practical application, both heat and mechanical (attrition grinding) pretreatment were found to substantially enhance carbonation reactivity. Unfortunately, these processes are too energy intensive to be cost-effective in their present form. In this project we explored the potential that utilizing power plant waste heat (e.g., available up to {approx}200-250 C) during mechanical activation (i.e., thermomechanical activation) offers to enhance serpentine mineral carbonation, while reducing pretreatment energy consumption and process cost. This project was carried out in collaboration with the Albany Research Center (ARC) to maximize the insight into the potential thermomechanical activation offers. Lizardite was selected as the model serpentine material for investigation, due to the relative structural simplicity of its lamellar structure when compared with the corrugated and spiral structures of antigorite and chrysotile, respectively. Hot-ground materials were prepared as a function of grinding temperature, time, and intensity. Carbonation reactivity was explored using the standard ARC serpentine carbonation test (155 C, 150 atm CO{sub 2}, and 1 hr). The product feedstock and carbonation materials were investigated via a battery of techniques, including X-ray powder diffraction, electron microscopy, thermogravimetric and differential thermal, BET, elemental, and infrared analysis. The incorporation of low-level heat with moderate mechanical activation (i.e., thermomechanical activation) was found to be able to substantially enhance serpentine carbonation reactivity in comparison with moderate mechanical activation alone. Increases in the extent of carbonation of over 70% have been observed in this feasibility study, indicating thermomechanical activation offers substantial potential to lower process cost. Investigations of the thermomechanically activated materials that formed indicate adding low-level heat during moderately intense lizardite mechanical activation promotes (1) energy absorption during activation, (2) structural disorder, and (3) dehydroxylation, as well as carbonation reactivity, with the level of energy absorption, structural disorder and dehydroxylation generally increasing with increasing activation temperature. Increasing activation temperatures were also associated with decreasing surface areas and water absorptive capacities for the activated product materials. The above decreases in surface area and water absorption capacity can be directly correlated with enhanced particle sintering during thermomechanical activation, as evidenced by electron microscopy observation. The level of induced structural disorder appears to be a key parameter in enhancing carbonation reactivity. However, particle sintering may contribute to reduced reactivity. The effectiveness of thermomechanical activation at enhancing carbonation reactivity appears to be a complicated function of a variety of process parameters, including grinding intensity, feedstock-to-media ratio, time, temperature, etc