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All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Machine Learning Inference of Random Medium Properties

Earth materials are heterogeneous across a range of spatial scales, but the resolvability of small structures is limited by sparse data coverage, noise, bandlimitedness, and other difficulties. In practice, heterogeneities below a certain size cannot be recovered from seismic data except through statistical medium descriptions, which even then can be difficult to uniquely determine. To improve the characterization of such heterogeneities, we develop a novel supervised machine learning (ML) model that provides insight about the recoverability of statistical medium properties from elastic waveform data and succeeds despite cycle-skipping and other challenges well known from elastic waveform inversion. We demonstrate the approach using random media generated by superimposing self-affine random variations on homogeneous and layered background structures. After training on sparsely-recorded, high-frequency waveforms from hundreds of different random medium realizations, we show the ability of our ML model to recover correlation lengths and other statistical properties of interest to near-surface and crustal seismology, among other fields. For frequency passbands and spatial offsets encountered in seismology, Gaussian correlation lengths and the amplitude of the random variations relative to the background model are recovered even in challenging scenarios involving unknown medium parameters, complex crustal structures, and low signal-to-noise ratio. In comparison, von Kármán correlation lengths, which are related to larger-wavelength variations of the medium than Gaussian correlation lengths, are not as well recovered. These results provide one of the first and most systematic investigations of the recoverability of statistical properties of heterogeneities below the resolution limit of deterministic seismic tomography, and suggest practical ML strategies for high-frequency waveform seismology.

58 GEOSCIENCES↗
NASA NTRS1982

Electrohydrodynamic (EHD) stimulation of jet breakup

Electrohydrodynamic (EHD) excitation of liquid jets offers an alternative to piezoelectric excitation without the complex frequency response caused by piezoelectric and mechanical resonances. In an EHD exciter, an electrode near the nozzle applies an alternating Coulomb force to the jet surface, generating a disturbance which grows until a drop breaks off downstream. This interaction is modelled quite well by a linear, long wave model of the jet together with a cylindrical electric field. The breakup length, measured on a 33 micrometer jet, agrees quite well with that predicted by the theory, and increases with the square of the applied voltage, as expected. In addition, the frequency response is very smooth, with pronounced nulls occurring only at frequencies related to the time which the jet spends inside the exciter.

Crowley, J. M.↗
NASA NTRS1982

The accretional heating of the terrestrial planets - A review

Accretional heating in forming planets results from the transfer of kinetic energy of objects striking the proto-planet surface. By accounting for all energy transfer for every cratering event it is theoretically possible to determine the thermal state of newly-formed planets. Various models of the thermodynamics of planetary formation are presented, ranging from the simple to the complex. Few definite conclusions can be drawn from the theoretical models, except that larger terrestrial planets were melted by their formation, cores being formed during formation. Mars may have been extensively heated, core formation in that case being contemporaneous with accretion. Mercury was unlikely to have been subject to much bombardment by planetesimals from other zones, and its core may not have its origin in accretional heat. The moon may have been completely or slightly melted, depending on the nature of the late formation of the earth and Venus.

Ransford, G. A.↗
NASA NTRS1993

Numerical computation of complex multi-body Navier-Stokes flows with applications for the integrated Space Shuttle launch vehicle

An enhanced grid system for the Space Shuttle Orbiter was built by integrating CAD definitions from several sources and then generating the surface and volume grids. The new grid system contains geometric components not modeled previously plus significant enhancements on geometry that has been modeled in the old grid system. The new orbiter grids were then integrated with new grids for the rest of the launch vehicle. Enhancements were made to the hyperbolic grid generator HYPGEN and new tools for grid projection, manipulation, and modification, Cartesian box grid and far field grid generation and post-processing of flow solver data were developed.

Chan, William M.↗
NASA NTRS2004

A Comparison of Local Variance, Fractal Dimension, and Moran's I as Aids to Multispectral Image Classification

The accuracy of traditional multispectral maximum-likelihood image classification is limited by the skewed statistical distributions of reflectances from the complex heterogenous mixture of land cover types in urban areas. This work examines the utility of local variance, fractal dimension and Moran's I index of spatial autocorrelation in segmenting multispectral satellite imagery. Tools available in the Image Characterization and Modeling System (ICAMS) were used to analyze Landsat 7 imagery of Atlanta, Georgia. Although segmentation of panchromatic images is possible using indicators of spatial complexity, different land covers often yield similar values of these indices. Better results are obtained when a surface of local fractal dimension or spatial autocorrelation is combined as an additional layer in a supervised maximum-likelihood multispectral classification. The addition of fractal dimension measures is particularly effective at resolving land cover classes within urbanized areas, as compared to per-pixel spectral classification techniques.

Emerson, Charles W.↗
NASA NTRS2011

Toward Supersonic Retropropulsion CFD Validation

This paper begins the process of verifying and validating computational fluid dynamics (CFD) codes for supersonic retropropulsive flows. Four CFD codes (DPLR, FUN3D, OVERFLOW, and US3D) are used to perform various numerical and physical modeling studies toward the goal of comparing predictions with a wind tunnel experiment specifically designed to support CFD validation. Numerical studies run the gamut in rigor from code-to-code comparisons to observed order-of-accuracy tests. Results indicate that this complex flowfield, involving time-dependent shocks and vortex shedding, design order of accuracy is not clearly evident. Also explored is the extent of physical modeling necessary to predict the salient flowfield features found in high-speed Schlieren images and surface pressure measurements taken during the validation experiment. Physical modeling studies include geometric items such as wind tunnel wall and sting mount interference, as well as turbulence modeling that ranges from a RANS (Reynolds-Averaged Navier-Stokes) 2-equation model to DES (Detached Eddy Simulation) models. These studies indicate that tunnel wall interference is minimal for the cases investigated; model mounting hardware effects are confined to the aft end of the model; and sparse grid resolution and turbulence modeling can damp or entirely dissipate the unsteadiness of this self-excited flow.

Kleb, Bil↗
NASA NTRS2015

Solid Rocket Motor Combustion Instability Modeling in COMSOL Multiphysics

Combustion instability modeling of Solid Rocket Motors (SRM) remains a topic of active research. Many rockets display violent fluctuations in pressure, velocity, and temperature originating from the complex interactions between the combustion process, acoustics, and steady-state gas dynamics. Recent advances in defining the energy transport of disturbances within steady flow-fields have been applied by combustion stability modelers to improve the analysis framework. Employing this more accurate global energy balance requires a higher fidelity model of the SRM flow-field and acoustic mode shapes. The current industry standard analysis tool utilizes a one dimensional analysis of the time dependent fluid dynamics along with a quasi-three dimensional propellant grain regression model to determine the SRM ballistics. The code then couples with another application that calculates the eigenvalues of the one dimensional homogenous wave equation. The mean flow parameters and acoustic normal modes are coupled to evaluate the stability theory developed and popularized by Culick. The assumption of a linear, non-dissipative wave in a quiescent fluid remains valid while acoustic amplitudes are small and local gas velocities stay below Mach 0.2. The current study employs the COMSOL Multiphysics finite element framework to model the steady flow-field parameters and acoustic normal modes of a generic SRM. This work builds upon previous efforts to verify the use of the acoustic velocity potential equation (AVPE) laid out by Campos. The acoustic velocity potential (psi) describing the acoustic wave motion in the presence of an inhomogeneous steady high-speed flow is defined by, del squared psi - (lambda/c) squared psi - M x [M x del((del)(psi))] - 2((lambda)(M)/c + M x del(M) x (del)(psi) - 2(lambda)(psi)[M x del(1/c)] = 0. with M as the Mach vector, c as the speed of sound, and λ as the complex eigenvalue. The study requires one way coupling of the CFD High Mach Number Flow (HMNF) and mathematics module. The HMNF module evaluates the gas flow inside of a SRM using St. Robert's law to model the solid propellant burn rate, slip boundary conditions, and the supersonic outflow condition. Results from the HMNF model are verified by comparing the pertinent ballistics parameters with the industry standard code outputs (i.e. pressure drop, axial velocity, exit velocity). These results are then used by the coefficient form of the mathematics module to determine the complex eigenvalues of the AVPE. The mathematics model is truncated at the nozzle sonic line, where a zero flux boundary condition is self-satisfying. The remaining boundaries are modeled with a zero flux boundary condition, assuming zero acoustic absorption on all surfaces. The one way coupled analysis is perform four times utilizing geometries determined through traditional SRM modeling procedures. The results of the steady-state CFD and AVPE analyses are used to calculate the linear acoustic growth rate as is defined by Flandro and Jacob. In order to verify the process implemented within COMSOL we first employ the Culick theory and compare the results with the industry standard. After the process is verified, the Flandro/Jacob energy balance theory is employed and results displayed.

Fischbach, S. R.↗
NASA NTRS2014

Calculation of Operations Efficiency Factors for Mars Surface Missions

The duration of a mission--and subsequently, the minimum spacecraft lifetime--is a key component in designing the capabilities of a spacecraft during mission formulation. However, determining the duration is not simply a function of how long it will take the spacecraft to execute the activities needed to achieve mission objectives. Instead, the effects of the interaction between the spacecraft and ground operators must also be taken into account. This paper describes a method, using "operations efficiency factors", to account for these effects for Mars surface missions. Typically, this level of analysis has not been performed until much later in the mission development cycle, and has not been able to influence mission or spacecraft design. Further, the notion of moving to sustainable operations during Prime Mission--and the effect that change would have on operations productivity and mission objective choices--has not been encountered until the most recent rover missions (MSL, the (now-cancelled) joint NASA-ESA 2018 Mars rover, and the proposed rover for Mars 2020). Since MSL had a single control center and sun-synchronous relay assets (like MER), estimates of productivity derived from MER prime and extended missions were used. However, Mars 2018's anticipated complexity (there would have been control centers in California and Italy, and a non-sun-synchronous relay asset) required the development of an explicit model of operations efficiency that could handle these complexities. In the case of the proposed Mars 2018 mission, the model was employed to assess the mission return of competing operations concepts, and as an input to component lifetime requirements. In this paper we provide examples of how to calculate the operations efficiency factor for a given operational configuration, and how to apply the factors to surface mission scenarios. This model can be applied to future missions to enable early effective trades between operations design, science mission planning, and spacecraft design.

Laubach, Sharon↗
DOE OSTI2024

Atmospheric pressure plasmas interacting with wet and dry microchannels: reverse surface ionization waves

Atmospheric pressure plasma jets (APPJs) are increasingly being used to functionalize polymers and dielectric materials for biomedical and biotechnology applications. Once such application is microfluidic labs-on-a-chip consisting of dielectric slabs with microchannel grooves hundreds of microns in width and depth. The periodic channels, an example of a complex surface, present challenges in terms of directly and uniformly exposing the surface to the plasma. In this paper, we discuss results from computational and experimental investigations of negative APPJs sustained in Ar/N 2 mixtures flowing into ambient air and incident onto a series of microchannels. Results from two-dimensional plasma hydrodynamics modeling are compared to experimental measurements of electric field and fast-camera imaging. The propagation of the plasma across dry microchannels largely consists of a sequence of surface ionization waves (SIWs) on the top ridges of the channels and bulk ionization waves (IWs) crossing over the channels. The IWs are directed into electric field enhanced vertices of the next ridge. The charging of these ridges produce reverse IWs responsible for the majority of the ionization. The propagation of the plasma across water filled microchannels evolve into hopping SIWs between the leading edges of the water channels, regions of electric enhancement due to polarization of the water. Positive, reverse IWs follow the pre-ionized path of the initial negative waves.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2023

A level-set immersed boundary method for reactive transport in complex topologies with moving interfaces

A simulation framework based on the level-set and the immersed boundary methods (LS-IBM) has been developed for reactive transport problems in porous media involving a moving solid-fluid interface. The interface movement due to surface reactions is tracked by the level-set method, while the immersed boundary method captures the momentum and mass transport at the interface. The proposed method is capable of accurately modeling transport near evolving boundaries in Cartesian grids. The framework formulation guarantees second order accuracy in space. Since the interface velocity is only defined at the moving boundary, an interface velocity propagation method is also proposed. The method can be applied to other moving interface problems of the “Stefan” type. Here, we validate the proposed LS-IBM both for flow and transport close to an immersed object with reactive boundaries as well as for crystal growth. Lastly, the proposed method provides a powerful tool to model more realistic problems involving moving reactive interfaces in complex domains.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
NASA NTRS2013

How Cities Breathe: Ground-Referenced, Airborne Hyperspectral Imaging Precursor Measurements To Space-Based Monitoring

Methane's (CH4) large global warming potential (Shindell et al., 2012) and likely increasing future emissions due to global warming feedbacks emphasize its importance to anthropogenic greenhouse warming (IPCC, 2007). Furthermore, CH4 regulation has far greater near-term climate change mitigation potential versus carbon dioxide CO2, the other major anthropogenic Greenhouse Gas (GHG) (Shindell et al., 2009). Uncertainties in CH4 budgets arise from the poor state of knowledge of CH4 sources - in part from a lack of sufficiently accurate assessments of the temporal and spatial emissions and controlling factors of highly variable anthropogenic and natural CH4 surface fluxes (IPCC, 2007) and the lack of global-scale (satellite) data at sufficiently high spatial resolution to resolve sources. Many important methane (and other trace gases) sources arise from urban and mega-urban landscapes where anthropogenic activities are centered - most of humanity lives in urban areas. Studying these complex landscape tapestries is challenged by a wide and varied range of activities at small spatial scale, and difficulty in obtaining up-to-date landuse data in the developed world - a key desire of policy makers towards development of effective regulations. In the developing world, challenges are multiplied with additional political access challenges. As high spatial resolution satellite and airborne data has become available, activity mapping applications have blossomed - i.e., Google maps; however, tap a minute fraction of remote sensing capabilities due to limited (three band) spectral information. Next generation approaches that incorporate high spatial resolution hyperspectral and ultraspectral data will allow detangling of the highly heterogeneous usage megacity patterns by providing diagnostic identification of chemical composition from solids (refs) to gases (refs). To properly enable these next generation technologies for megacity include atmospheric radiative transfer modeling the complex and often aerosol laden, humid, urban microclimates, atmospheric transport and profile monitoring, spatial resolution, temporal cycles (diurnal and seasonal which involve interactions with the surrounding environment diurnal and seasonal cycles) and representative measurement approaches given traffic realities. Promising approaches incorporate contemporaneous airborne remote sensing and in situ measurements, nocturnal surface surveys, with ground station measurement

Leifer, Ira↗
NASA NTRS2007

Characteristics of Boundary Layer Transition in a Multi-Stage Low-Pressure Turbine

An experimental investigation of boundary layer transition in a multi-stage turbine has been completed using surface-mounted hot-film sensors. Tests were carried out using the two-stage Low Speed Research Turbine of the Aerodynamics Research Laboratory of GE Aircraft Engines. Blading in this facility models current, state-of-the-art low pressure turbine configurations. The instrumentation technique involved arrays of densely-packed hot-film sensors on the surfaces of second stage rotor and nozzle blades. The arrays were located at mid-span on both the suction and pressure surfaces. Boundary layer measurements were acquired over a complete range of relevant Reynolds numbers. Data acquisition capabilities provided means for detailed data interrogation in both time and frequency domains. Data indicate that significant regions of laminar and transitional boundary layer flow exist on the rotor and nozzle suction surfaces. Evidence of relaminarization both near the leading edge of the suction surface and along much of the pressure surface was observed. Measurements also reveal the nature of the turbulent bursts occuring within and between the wake segments convecting through the blade row. The complex character of boundary layer transition resulting from flow unsteadiness due to nozzle/nozzle, rotor/nozzle, and nozzle/rotor wake interactions are elucidated using these data. These measurements underscore the need to provide turbomachinery designers with models of boundary layer transition to facilitate accurate prediction of aerodynamic loss and heat transfer.

Wisler, Dave↗
DOE OSTI2020

Microstructure Generation via Generative Adversarial Network for Heterogeneous, Topologically Complex 3D Materials

Using a large-scale, experimentally captured 3D microstructure dataset, we implement the generative adversarial network (GAN) framework to learn and generate 3D microstructures of solid oxide fuel cell electrodes. The generated microstructures are visually, statistically, and topologically realistic, with distributions of microstructural parameters, including volume fraction, particle size, surface area, tortuosity, and triple phase boundary density, being highly similar to those of the original microstructure. These results are compared and contrasted with those from an established, grain-based generation algorithm (DREAM.3D). Importantly, simulations of electrochemical performance, using a locally resolved finite element model, demonstrate that the GAN generated microstructures closely match the performance distribution of the original, while DREAM.3D leads to significant differences. Finally, the ability of the generative machine learning model to recreate microstructures with high fidelity suggests that the essence of complex microstructures may be captured and represented in a compact and manipulatable form.

36 MATERIALS SCIENCE↗
NASA NTRSDate not supplied

Technology Assessment and Modelling of Three Terminal Tandem Solar Cells for In-Space Utilization

NASA seeks a sustained human presence on the lunar surface. High-efficiency and resilient energy systems are critical to supporting habitats, scientific outposts, and lunar surface operations. Photovoltaics have long been the backbone of space power systems, transitioning from silicon solar cells to multi-junction III-V solar cells, which now dominate state-of-the-art (SOA) technology. Multi-junction cells achieve high efficiency by layering semiconductors, each absorbing a specific portion of the solar spectrum. However, efficiency gains are increasingly constrained by device physics and manufacturing complexity. Additionally, higher-order junctions pose challenges for accurate modelling and performance characterization due to difficulties in replicating the AM0 spectrum.

solar cells↗
DOE OSTI2020

Projecting Antarctica's contribution to future sea level rise from basal ice shelf melt using linear response functions of 16 ice sheet models (LARMIP-2)

Abstract. The sea level contribution of the Antarctic ice sheet constitutes a large uncertainty in future sea level projections. Here we apply a linear response theory approach to 16 state-of-the-art ice sheet models to estimate the Antarctic ice sheet contribution from basal ice shelf melting within the 21st century. The purpose of this computation is to estimate the uncertainty of Antarctica's future contribution to global sea level rise that arises from large uncertainty in the oceanic forcing and the associated ice shelf melting. Ice shelf melting is considered to be a major if not the largest perturbation of the ice sheet's flow into the ocean. However, by computing only the sea level contribution in response to ice shelf melting, our study is neglecting a number of processes such as surface-mass-balance-related contributions. In assuming linear response theory, we are able to capture complex temporal responses of the ice sheets, but we neglect any self-dampening or self-amplifying processes. This is particularly relevant in situations in which an instability is dominating the ice loss. The results obtained here are thus relevant, in particular wherever the ice loss is dominated by the forcing as opposed to an internal instability, for example in strong ocean warming scenarios. In order to allow for comparison the methodology was chosen to be exactly the same as in an earlier study (Levermann et al., 2014) but with 16 instead of 5 ice sheet models. We include uncertainty in the atmospheric warming response to carbon emissions (full range of CMIP5 climate model sensitivities), uncertainty in the oceanic transport to the Southern Ocean (obtained from the time-delayed and scaled oceanic subsurface warming in CMIP5 models in relation to the global mean surface warming), and the observed range of responses of basal ice shelf melting to oceanic warming outside the ice shelf cavity. This uncertainty in basal ice shelf melting is then convoluted with the linear response functions of each of the 16 ice sheet models to obtain the ice flow response to the individual global warming path. The model median for the observational period from 1992 to 2017 of the ice loss due to basal ice shelf melting is 10.2 mm, with a likely range between 5.2 and 21.3 mm. For the same period the Antarctic ice sheet lost mass equivalent to 7.4 mm of global sea level rise, with a standard deviation of 3.7 mm (Shepherd et al., 2018) including all processes, especially surface-mass-balance changes. For the unabated warming path, Representative Concentration Pathway 8.5 (RCP8.5), we obtain a median contribution of the Antarctic ice sheet to global mean sea level rise from basal ice shelf melting within the 21st century of 17 cm, with a likely range (66th percentile around the mean) between 9 and 36 cm and a very likely range (90th percentile around the mean) between 6 and 58 cm. For the RCP2.6 warming path, which will keep the global mean temperature below 2 ∘C of global warming and is thus consistent with the Paris Climate Agreement, the procedure yields a median of 13 cm of global mean sea level contribution. The likely range for the RCP2.6 scenario is between 7 and 24 cm, and the very likely range is between 4 and 37 cm. The structural uncertainties in the method do not allow for an interpretation of any higher uncertainty percentiles. We provide projections for the five Antarctic regions and for each model and each scenario separately. The rate of sea level contribution is highest under the RCP8.5 scenario. The maximum within the 21st century of the median value is 4 cm per decade, with a likely range between 2 and 9 cm per decade and a very likely range between 1 and 14 cm per decade.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2024

Goethite and Hematite Nucleation and Growth from Ferrihydrite: Effects of Oxyanion Surface Complexes

The presence of oxyanions, such as nitrate (NO 3 – ) and phosphate (PO 4 3– ), regulates the nucleation and growth of goethite (Gt) and hematite (Hm) during the transformation of ferrihydrite (Fh). Our previous studies showed that oxyanion surface complexes control the rate and pathway of Fh transformation to Gt and Hm. However, how oxyanion surface complexes control the mechanism of Gt and Hm nucleation and growth during the Fh transformation is still unclear. Here, we used synchrotron scattering methods and cryogenic transmission electron microscopy to investigate the effects of NO 3 – outer-sphere complexes and PO 4 3– inner-sphere complexes on the mechanism of Gt and Hm formation from Fh. Our TEM results indicated that Gt particles form through a two-step model in which Fh particles first transform to Gt nanoparticles and then crystallographically align and grow to larger particles by oriented attachment (OA). In contrast, for the formation of Hm, imaging shows that Fh particles first aggregate and then transform to Hm through interface nucleation. This is consistent with our X-ray scattering results, which demonstrate that NO 3 – outer-sphere and PO 4 3– inner-sphere complexes promote the formation of Gt and Hm, respectively. These results have implications for understanding the coupled interactions of oxyanions and iron oxy-hydroxides in Earth-surface environments.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2023

Near-continuum, hypersonic oxygen flow over a double cone simulated by direct simulation Monte Carlo informed from quantum chemistry

A large-scale, fully resolved direct simulation Monte Carlo (DSMC) computation of a non-equilibrium, reactive flow of pure oxygen over a double cone is presented. Under the simulated near-continuum conditions, the computational demands are shown to be significant because of the wide range of length scales that must be resolved. Therefore, robust grid adaption capabilities and efficient parallelization of the Stochastic PArallel Rarefied-gas Time-accurate Analyzer (SPARTA) code that is utilized in this work are essential. The thermochemical and transport collision models were selected for efficiency and simplicity. First-principles data, obtained from the highly accurate direct molecular simulation method, were used to inform the collision models’ parameters. Importantly, because SPARTA implements molecular collision models using collision-specific energies, the resulting macroscopic relaxation rates were evaluated a posteriori via zero-dimensional heat bath simulations. The comparisons of surface properties, namely heat flux and pressure, show very close agreement with previous computational fluid dynamics (CFD) results. Differences with the measurements were found to be similar to the CFD simulations. The unresolved discrepancy with the measurements could be due to inconsistent free stream conditions with the actual experimental data or missing physical phenomena altogether, for example atomic and molecular oxygen electronically excited states, three-dimensional effects, or more complex gas–surface interactions. As shown in this work, the advantages of obtaining a DSMC particle solution for these flows reside in the method's ability to be directly informed from first principles and to seamlessly describe internal energy non-equilibrium for all modes. With the advent of exascale computing and beyond, particle methods will be an increasingly important tool to verify the validity of physical assumptions in reduced-order models via fully resolved, experimental-scale simulations, down to the level of molecular-level distributions.

Mechanics↗
DOE OSTI2024

Ca-dimers, solvent layering, and dominant electrochemically active species in Ca(BH4)2 in THF

Abstract Divalent ions (Mg, Ca, and Zn) are being considered as competitive, safe, and earth-abundant alternatives to Li-ion electrochemistry, but present challenges for stable cycling due to undesirable interfacial phenomena. We explore the formation of electroactive species in the electrolyte Ca(BH 4 ) 2 ∣THF using molecular dynamics coupled with a continuum model of bulk and interfacial speciation. Free-energy analysis and unsupervised learning indicate a majority population of neutral Ca dimers and monomers with diverse molecular conformations and an order of magnitude lower concentration of the primary electroactive charged species – the monocation, $${\rm{CaBH}}_{4}^{+}$$ CaBH 4 + – produced via disproportionation of neutral complexes. Dense layering of THF molecules within ~1 nm of the electrode surface strongly modulates local electrolyte species populations. A dramatic increase in monocation population in this interfacial zone is induced at negative bias. We see no evidence for electrochemical activity of fully-solvated Ca 2+ . The consequences for performance are discussed in light of this molecular-scale insight.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗