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At least 199 records · Page 11

A Proposed Mechanism for the Thermal Denaturation of a Recombinant Bacillus Halmapalus Alpha-amylase - the Effect of Calcium Ions

The thermal stability of a recombinant alpha-amylase from Bacillus halmapalus alpha-amylase (BHA) has been investigated using circular dichroism spectroscopy (CD) and differential scanning calorimetry (DSC). This alpha-amylase is homologous to other Bacillus alpha-amylases where previous crystallographic studies have identified the existence of 3 calcium binding sites in the structure. Denaturation of BHA is irreversible with a Tm of approximately 89 C, and DSC thermograms can be described using a one-step irreversible model. A 5 C increase in T(sub m) in the presence of 10 fold excess CaCl2 was observed. However, a concomitant increase in the tendency to aggregate was also observed. The presence of 30-40 fold excess calcium chelator (EDTA or EGTA) results in a large destabilization of BHA corresponding to about 40 C lower T(sub m), as determined by both CD and DSC. Ten fold excess EGTA reveals complex DSC thermograms corresponding to both reversible and irreversible transitions, which possibly originate from different populations of BHA:calcium complexes. The observations in the present study have, in combination with structural information of homologous alpha-amylases, provided the basis for the proposal of a simple denaturation mechanism of BHA. The proposed mechanism describes the irreversible thermal denaturation of different BHA:calcium complexes and the calcium binding equilibrium involved. Furthermore, the model accounts for a temperature induced reversible structural change associated with calcium binding.

Nielsen, Anders D.↗

Polarimetric and Multi-Doppler Radar Observations of Electrified and Unelectrified Wildfire Smoke Plumes

Pyrocumulus clouds above three Colorado wildfires (Hewlett Gulch, High Park, and Waldo Canyon; all occurred during summer 2012) electrified and produced small intracloud discharges whenever the smoke plumes grew to high altitudes (over 10 km above mean sea level, or MSL). This occurred during periods of rapid wildfire growth, as indicated by the shortwave infrared channel on a geostationary satellite, as well as by incident reports. In the Hewlett Gulch case, the fire growth led to increased updrafts within the plume, as inferred by multiple‐ Doppler radar syntheses, which led to the vertical development and subsequent electrification ‐ a life cycle as short as 30 minutes. The lightning, detected by a threedimensional lightning mapping network, was favored in high‐altitude regions (~10 km MSL) containing modest reflectivities (25 dBZ and lower), ~0 dB differential reflectivity, and reduced correlation coefficient (~0.6‐0.7). This indicated the likely presence of ice particles (crystals and aggregates, possibly rimed) mixed with ash. Though neither multiple‐Doppler nor polarimetric observations were available during the electrification of the High Park and Waldo Canyon plumes, their NEXRAD observations showed reflectivity structures consistent with Hewlett Gulch. In addition, polarimetric and multiple‐Doppler scanning of unelectrified High Park plumes indicated only irregularly shaped ash, and not ice, was present (i.e., reflectivities < 25 dBZ, differential reflectivity > 5 dB, correlation < 0.4), and there was no broaching of the 10 km altitude. Based on these results, the electrification likely was caused by ice‐based processes that did not involve significant amounts of graupel. The results demonstrate the scientific value of multiple‐Doppler and polarimetric radar observations of wildfire smoke plumes ‐ including the ability to distinguish between regions of pure hydrometeors, regions of pure ash, and mixtures of both ‐ and also suggest a possible new application for lightning data in monitoring wildfires.

Lang, Timothy J.↗

On the Electrification of Pyrocumulus Clouds

The electrification (or lack thereof) of pyrocumulus clouds is examined for several different wildfires that occurred during 2012‐2013. For example, pyrocumulus clouds above three Colorado wildfires (Hewlett Gulch, High Park, and Waldo Canyon; all occurred during summer 2012) electrified and produced small intracloud discharges whenever the smoke plumes grew to high altitudes (over 10 km above mean sea level, or MSL). This occurred during periods of rapid wildfire growth, as indicated by the shortwave infrared channel on a geostationary satellite, as well as by incident reports. In the Hewlett Gulch case, the fire growth led to increased updrafts within the plume, as inferred by multiple‐Doppler radar syntheses, which led to the vertical development and subsequent electrification ‐ a life cycle as short as 30 minutes. The lightning, detected by a three‐dimensional lightning mapping network, was favored in high‐altitude regions (~10 km MSL) containing modest reflectivities (25 dBZ and lower), ~0 dB differential reflectivity, and reduced correlation coefficient (~0.6‐0.7). This indicated the likely presence of ice particles (crystals and aggregates, possibly rimed) mixed with ash. Though neither multiple‐Doppler nor polarimetric observations were available during the electrification of the High Park and Waldo Canyon plumes, their NEXRAD observations showed reflectivity structures consistent with Hewlett Gulch. In addition, polarimetric and multiple‐Doppler scanning of unelectrified High Park plumes indicated only irregularly shaped ash, and not ice, was present (i.e., reflectivities < 25 dBZ, differential reflectivity > 5 dB, correlation < 0.4), and there was no broaching of the 10 km altitude. Based on these results, the electrification likely was caused by ice‐based processes that did not involve significant amounts of graupel. Results for pyrocumulus clouds above notable 2013 wildfires that also experienced rapid growth (e.g., Black Forest, Yarnell Hill, West Fork, Tres Lagunas, etc.) will be compared against the 2012 cases, with special emphasis on polarimetric NEXRAD and available lightning measurements, in order to better understand the physical processes responsible for pyrocumulus electrification.

Lang, Timothy J.↗

A Lightweight I/O Scheme to Facilitate Spatial and Temporal Queries of Scientific Data Analytics

In the era of petascale computing, more scientific applications are being deployed on leadership scale computing platforms to enhance the scientific productivity. Many I/O techniques have been designed to address the growing I/O bottleneck on large-scale systems by handling massive scientific data in a holistic manner. While such techniques have been leveraged in a wide range of applications, they have not been shown as adequate for many mission critical applications, particularly in data post-processing stage. One of the examples is that some scientific applications generate datasets composed of a vast amount of small data elements that are organized along many spatial and temporal dimensions but require sophisticated data analytics on one or more dimensions. Including such dimensional knowledge into data organization can be beneficial to the efficiency of data post-processing, which is often missing from exiting I/O techniques. In this study, we propose a novel I/O scheme named STAR (Spatial and Temporal AggRegation) to enable high performance data queries for scientific analytics. STAR is able to dive into the massive data, identify the spatial and temporal relationships among data variables, and accordingly organize them into an optimized multi-dimensional data structure before storing to the storage. This technique not only facilitates the common access patterns of data analytics, but also further reduces the application turnaround time. In particular, STAR is able to enable efficient data queries along the time dimension, a practice common in scientific analytics but not yet supported by existing I/O techniques. In our case study with a critical climate modeling application GEOS-5, the experimental results on Jaguar supercomputer demonstrate an improvement up to 73 times for the read performance compared to the original I/O method.

Temporal Queries↗

Measurements and Modeling of Soot Formation and Radiation in Microgravity Jet Diffusion Flames

This is a computational and experimental study for soot formation and radiative heat transfer in jet diffusion flames under normal gravity (1-g) and microgravity (0-g) conditions. Instantaneous soot volume fraction maps are measured using a full-field imaging absorption technique developed by the authors. A compact, self-contained drop rig is used for microgravity experiments in the 2.2-second drop tower facility at NASA Lewis Research Center. On modeling, we have coupled flame structure and soot formation models with detailed radiation transfer calculations. Favre-averaged boundary layer equations with a k-e-g turbulence model are used to predict the flow field, and a conserved scalar approach with an assumed Beta-pdf are used to predict gaseous species mole fraction. Scalar transport equations are used to describe soot volume fraction and number density distributions, with formation and oxidation terms modeled by one-step rate equations and thermophoretic effects included. An energy equation is included to couple flame structure and radiation analyses through iterations, neglecting turbulence-radiation interactions. The YIX solution for a finite cylindrical enclosure is used for radiative heat transfer calculations. The spectral absorption coefficient for soot aggregates is calculated from the Rayleigh solution using complex refractive index data from a Drude- Lorentz model. The exponential-wide-band model is used to calculate the spectral absorption coefficient for H20 and C02. It is shown that when compared to results from true spectral integration, the Rosseland mean absorption coefficient can provide reasonably accurate predictions for the type of flames studied. The soot formation model proposed by Moss, Syed, and Stewart seems to produce better fits to experimental data and more physically sound than the simpler model by Khan et al. Predicted soot volume fraction and temperature results agree well with published data for a normal gravity co-flow laminar flames and turbulent jet flames. Predicted soot volume fraction results also agree with our data for 1-g and 0-g laminar jet names as well as 1-g turbulent jet flames.

Ku, Jerry C.↗

Resistance to Sliding on Atomic Scales

The structure and stability of agglomerates of micron-sized particles is determined by the mechanical properties of the individual contacts between the constituent particles. In this paper we study the possibility of aggregate rearrangements by sliding. Since the contacts between (sub)micron particles are only a few hundred atoms in diameter, processes on atomic levels will play the dominating roll. We study a theoretical model of sliding friction for surfaces that are either flat or contain steps in their grids. The results show that sliding over flat surfaces may produce a large range of friction coefficients, including zero if the adhesive forces are small compared to the binding forces inside a body. However, both grid alignment and steps in the surface will lead to high values for friction. These processes combined virtually eliminate the possibility of sliding in a collision of two (sub)micron sized particles at velocities low enough for sticking to occur. On the other hand we show that in collisions between aggregates sliding may be an important factor for energy dissipation and compaction.

Dominik, C.↗

Modeling the surface and interior structure of comet nuclei using a multidisciplinary approach

The goal was to investigate the structural properties of the surface of comet nucleus and how the surface should change with time under effect of solar radiation. The basic model that was adopted was that the nucleus is an aggregate of frosty particles loosely bound together, so that it is essentially a soil. The nucleus must mostly be composed of dust particles. The observed mass ratios of dust to gas in the coma is never much greater than unity, but this ratio is probably a much lower limit than that of the nucleus because it is vastly easier to remove the gaseous component by sublimation than by carrying off the dust. Therefore the described models assumed that the particles in the soil were frost covered grains of submicron basic size, closely resembling the interstellar grains. The surface properties of such a nucleus under the effects of heating and cooling as the nucleus approaches and recedes from the Sun generally characterized.

Odell, C. R.↗

Simulation of Peptides at Aqueous Interfaces

Behavior of peptides at water-membrane interfaces is of great interest in studies on cellular transport and signaling, membrane fusion, and the action of toxins and antibiotics. Many peptides, which exist in water only as random coils, can form sequence-dependent, ordered structures at aqueous interfaces, incorporate into membranes and self-assembly into functional units, such as simple ion channels. Multi -nanosecond molecular dynamics simulations have been carried out to study the mechanism and energetics of interfacial folding of both non-polar and amphiphilic peptides, their insertion into membranes and association into higher-order structures. The simulations indicate that peptides fold non-sequentially, often through a series of amphiphilic intermediates. They further incorporate into the membrane in a preferred direction as folded monomers, and only then aggregate into dimers and, possibly, further into "dimers of dimers".

Pohorille, Andrew↗

Locally stabilizable large-scale systems

A class of large scale linear systems, stabilizable by local feedback control applied around each decoupled subsystem, is established. The control scheme, outlined in the paper, is based upon the decomposition-aggregation method, and involves only operations on the subsystem level. The systems, stabilized by the proposed method, have a tolerance to a wide class of non-linearities, and are reliable with respect to the structural perturbations.

Vukcevic, M. B.↗

Porosity and Variations in Microgravity Aerogel Nano-Structures: New Laser Speckle Characterization Methods - 2

The transition from sol to gel is a process that is critical to the properties of engineered nanomaterials, but one with few available techniques for observing the dynamic processes occurring during the evolution of the gel network. Specifically, the observation of various cluster aggregation models, such as diffusion-limited and reaction-limited cluster growth can be quite difficult. This can be rather important as the actual aggregation model can dramatically influence the mechanical properties of gels, and is significantly affected by the presence of convective flows, or their absence in microgravity. We have developed two new non-intrusive optical methods for observing the aggregation processes within gels in real time. These make use of the dynamic behavior of laser speckle patterns produced when an intense laser source is passed through a gelling sol. The first method is a simplified time-correlation measurement, where the speckle pattern is observed using a CCD camera and information on the movement of the scattering objects is readily apparent. This approach is extremely sensitive to minute variations in the flow field as the observed speckle pattern is a diffraction-based image, and is therefore sensitive to motions within the sol on the order of the wavelength of the probing light. Additionally, this method has proven useful in determining a precise time for the gel-point, an event often difficult to measure. Monitoring the evolution of contrast within the speckle field is another method that has proven useful for studying aeration. In this case, speckle contrast is dependent upon the size (correlation length) and number of scattering centers, increasing with increasing size, and decreasing with increasing numbers. The dynamic behavior of cluster growth in gels causes both of these to change simultaneously with time, the exact rate of which is determined by the specific aggregation model involved. Actual growth processes can now be observed, and the effects of varying gravity fields on the growth processes qualitatively described. Results on preliminary ground-based measurements have been obtained.

Hunt, A. J.↗

Structure and origin of cometary nuclei

There is strong evidence that a comet nucleus consists of a single object whose basic structure is Whipple's icy conglomerate. A number of cometary phenomena indicate that the nucleus is a low density, fragile object with a large degree of radial uniformity in structure and composition. Details of the ice-dust pattern are more uncertain. A working model is proposed which is based on theories of accumulation of larger objects from grains. This nucleus is a distorted spherical aggregate of a hierarchy of ice-dust cometesimals. These cometesimals retain some separate identity which lead to comet fragmentation when larger components break off. The outer layers of new comets were modified by cosmic ray irradiation in the Oort Cloud. The evidence for meteorite-comet association is steill controversial. Current dynamical studies do not seem to require a cometary source of meteorites.

Donn, B.↗

Presolar Materials in a Giant Cluster IDP of Probable Cometary Origin

Chondritic porous interplanetary dust particles (CP-IDPs) have been linked to comets by their fragile structure, primitive mineralogy, dynamics, and abundant interstellar materials. But differences have emerged between 'cometary' CP-IDPs and comet 81P/Wild 2 Stardust Mission samples. Particles resembling Ca-Al-rich inclusions (CAIs), chondrules, and amoeboid olivine aggregates (AOAs) in Wild 2 samples are rare in CP-IDPs. Unlike IDPs, presolar materials are scarce in Wild 2 samples. These differences may be due to selection effects, such as destruction of fine grained (presolar) components during the 6 km/s aerogel impact collection of Wild 2 samples. Large refractory grains observed in Wild 2 samples are also unlikely to be found in most (less than 30 micrometers) IDPs. Presolar materials provide a measure of primitive-ness of meteorites and IDPs. Organic matter in IDPs and chondrites shows H and N isotopic anomalies attributed to low-T interstellar or protosolar disk chemistry, where the largest anomalies occur in the most primitive samples. Presolar silicates are abundant in meteorites with low levels of aqueous alteration (Acfer 094 approximately 200 ppm) and scarce in altered chondrites (e.g. Semarkona approximately 20 ppm). Presolar silicates in minimally altered CP-IDPs range from approximately 400 ppm to 15,000 ppm, possibly reflecting variable levels of destruction in the solar nebula or statistical variations due to small sample sizes. Here we present preliminary isotopic and mineralogical studies of a very large CP-IDP. The goals of this study are to more accurately determine the abundances of presolar components of CP-IDP material for comparison with comet Wild 2 samples and meteorites. The large mass of this IDP presents a unique opportunity to accurately determine the abundance of pre-solar grains in a likely cometary sample.

Messenger, S.↗

Learning Based Edge Computing in Air-to-Air Communication Network

This paper studies learning-based edge computing and communication in a dynamic Air-to-Air Ad-hoc Network (AAAN). Due to spectrum scarcity, we assume the number of Air-to-Air (A2A) communication links is greater than that of the available frequency channels, such that some communication links have to share the same channel, causing co-channel interference. We formulate the joint channel selection and power control optimization problem to maximize the aggregate spectrum utilization efficiency under resource and fairness constraints. A distributed deep Q learning-based edge computing and communication algorithm is proposed to find the optimal solution. In particular, we design two different neural network structures and each communication link can converge to the optimal operation by exploiting only the local information from its neighbors, making it scalable to large networks. Finally, experimental results demonstrate the effectiveness of the proposed solution in various AAAN scenarios.

Zhe Wang↗

A Structural and Molecular Approach for the Study Biomarkers

Investigation of the nucleation and growth of crystals in both abiotic and biotic systems is critical to seemingly diverse disciplines of geology, biology, environmental science, and astrobiology. While there are abundant studies devoted to the determination of the structure and composition of inorganic crystals, as well as to the development of thermodynamic and kinetic models, it is only recently that research efforts have been directed towards understanding mineralization in biological systems (i.e., biomineralization). Biomineralization refers to the processes by which living organisms form inorganic solids. Studies of the processes of biomineralization under low temperature aqueous conditions have focused primarily on magnetite forming bacteria and shell forming marine organisms. Many of the biological building materials consist of inorganic minerals (calcium carbonate, calcium phosphate, silica or iron oxide) intricately combined with organic polymers (like proteins). More recently, efforts have been undertaken to explore the nature of biological activities in ancient rocks. In the absence of well-preserved microorganisms or genetic material required for the polmerase chain reaction (PCR) method in molecular phylogenetic studies, using biominerals as biomarkers offers an alternative approach for the recognition of biogenic activity in both terrestrial and extraterrestrial environments. The primary driving force in biomineralization is the interaction between organic and inorganic phases. Thus, the investigation of the ultrastructure and the nature of reactions at the molecular level occurring at the interface between inorganic and organic phases is essential to understanding the processes leading to the nucleation and growth of crystals. It is recognized that crystal surfaces can serve as the substrate for the organization of organic molecules that lead to the formation of polymers and other complex organic molecules, and in discussions of the origins of life, is referred to as organic synthesis on mineral surfaces. Furthermore, it is suggested that the interaction between mineral surfaces and simple organic molecules resulted in the formation of amino acids, RNA, and perhaps other more complex molecules such as proteins. On the other hand, in natural systems, it is recognized that functional groups on cell walls or membranes of microorganisms serve as sites of nucleation and crystallization. The precise replication of biominerals with controlled structure, morphology, size and texture is not confined to higher organisms as it also occurs in primitive prokaryotic cells such as magnetotactic bacteria and cyanobacteria. This suggests that the principal strategies of biomineralization were established early on in the evolutionary history of organisms. It is critical, therefore, to search for common mechanisms within diverse biological systems. One such common factor is the capability for organization and self-assembly. Organic macromolecules such as proteins and lipids can aggregate and polymerize forming membranes or extracellular matrix. At the organic-inorganic interface, several factors such as lattice geometry, polarity, stereochemistry and topography may act in concert to control nucleation and growth of crystals. Although several models have been proposed that discuss the significance of these factors for biomineralization, no comprehensive experimental data are available. In contrast to crystallization in exclusively inorganic systems, the kinetics of reaction and structural relationships between organic and inorganic phases in biominerals or biomimetic material is poorly understood. For example, it is not clear if the concept of epitactic growth (geometrical matching of unit cells at the interface of a secondary crystal growing on a primary crystal) applies to organic-inorganic systems. In contrast to inorganic templates that often have a smooth and rigid surface that promotes epitactic growth, biological substrates are usually rough and result in a large degree of mismatch. It is apparent that factors controlling the reaction at the crystal-matrix interface are strongly dependent upon the nature of the substrate. Therefore, characterization of the assembled organic surface and surface structure of the inorganic phase is crucial to understanding the processes of biomineralization. The focus of our research is the investigation of the processes leading to the nucleation and growth of crystals on both natural and synthetic systems through an interdisciplinary approach that integrates molecular biology, morphology and mineralogy using advanced preparation and analytical techniques. We have studied run-products, particularly magnetite, siderite and other carbonates, that resulted from extracellular biomineralization by extremophiles isolated from a variety of extreme environments ranging from permafrost to hydrothermal vent systems. The results of this study are critical to recognizing biomarkers in terrestrial and extraterrestrial environments.

Thomas-Keprta, Kathie↗

Degradation of Fe-Mg silicates in hot CO2 atmospheres: Applications to Venus

Experiments demonstrated that oxidation of ferromagnesian silicates and magnetite occurs when these minerals are heated at 800 C in 1 atmosphere of CO2, under which conditions hematite is thermodynamically stable. The 30 ppm oxygen impurity in CO2 presumably facilitates the oxidation of some of the ferrous iron initially present in the crystal structures of the minerals. Mossbauer spectral measurements reveal, however, that only CO2 degraded olivine and pigeonite is hematite formed as a magnetically ordered phase at ambient temperatures. In orthopyroxene, some of the ferric iron produced by oxidation is present as nanophase hematite which, because it remains superparamagnetic until 4.2 K, must exist as particles less than or equal to 4 nm in diameter. In the calcic pyroxenes much of the oxidized ferrous iron may still remain as structural Fe3(+) in the host silicates. Some ferric iron may also be present as unit cell sized Fe2O3 inclusions in the pyroxenes, or be segregated along cleavage planes, or be coating mineral grains. In these states of aggregation, the Fe2O3 is unidentifiable by x ray diffraction and in low temperature Mossbauer spectra. Applications of this research to the surface of Venus are discussed.

Straub, Darcy W.↗

Canopy reflectance modelling of semiarid vegetation

Three different types of remote sensing algorithms for estimating vegetation amount and other land surface biophysical parameters were tested for semiarid environments. These included statistical linear models, the Li-Strahler geometric-optical canopy model, and linear spectral mixture analysis. The two study areas were the National Science Foundation's Jornada Long Term Ecological Research site near Las Cruces, NM, in the northern Chihuahuan desert, and the HAPEX-Sahel site near Niamey, Niger, in West Africa, comprising semiarid rangeland and subtropical crop land. The statistical approach (simple and multiple regression) resulted in high correlations between SPOT satellite spectral reflectance and shrub and grass cover, although these correlations varied with the spatial scale of aggregation of the measurements. The Li-Strahler model produced estimated of shrub size and density for both study sites with large standard errors. In the Jornada, the estimates were accurate enough to be useful for characterizing structural differences among three shrub strata. In Niger, the range of shrub cover and size in short-fallow shrublands is so low that the necessity of spatially distributed estimation of shrub size and density is questionable. Spectral mixture analysis of multiscale, multitemporal, multispectral radiometer data and imagery for Niger showed a positive relationship between fractions of spectral endmembers and surface parameters of interest including soil cover, vegetation cover, and leaf area index.

Franklin, Janet↗

Investigation of Structure and Transport in Li-Doped Ionic Liquid Electrolytes: [pyr14][TFSI], [pyr13][FSI], [EMIM][BF4]

Ionic liquid electrolytes have been proposed as a means of improving the safety and cycling behavior of advanced lithium batteries; however, the properties of these electrolytes under high lithium doping are poorly understood. Here, we employ both polarizable molecular dynamics simulation and experiment to investigate the structure, thermodynamics and transport of three potential electrolytes, N-methyl-N-butylpyrrolidinium bis(trifluoromethylsufonyl)imide ([pyr14][TFSI]), N- methyl-N-propylpyrrolidinium bis(fluorosufonyl)imide ([pyr13][FSI]), and 1-ethyl-3-- methylimidazolium boron tetrafluoride ([EMIM][BF4]), as a function of Li (-) salt concentration and temperature. Structurally, Li(+) is shown to be solvated by three anion neighbors in [pyr14][TFSI] and four anion neighbors in both [pyr13][FSI] and [EMIM][BF4], and at all levels of xLi we find the presence of lithium aggregates. Furthermore, the computed density, diffusion, viscosity, and ionic conductivity show excellent agreement with experimental data. While the diffusion and viscosity exhibit a systematic decrease and increase, respectively, with increasing xLi, the contribution of Li(+) to ionic conductivity increases until reaching a saturation doping level of xLi 0.10. Comparatively, the Li(+) conductivity of [pyr14][TFSI] is an order of magnitude lower than that of the other liquids, which range between 0.1-0.3 mScm. The differences in Li(+) transport are reflected in the residence times of Li(+) with the anions, which are revealed to be much larger for [pyr14][TFSI] (up to 100 ns at the highest doping levels) than in either [EMIM][BF4] or [pyr13][FSI]. Finally, we comment on the relative kinetics of Li(+) transport in each liquid and we present strong evidence for transport through anion exchange (hopping) as opposed to the net motion of Li(+) with its solvation shell (vehicular).

ionic liquids↗

Investigation of Structure and Transport in Li-Doped Ionic Liquid Electrolytes: [pyr14][TFSI], [pyr13][FSI], [EMIM][BF4]

Ionic liquid electrolytes have been proposed as a means of improving the safety and cycling behavior of advanced lithium batteries; however, the properties of these electrolytes under high lithium doping are poorly understood. Here, we employ both polarizable molecular dynamics simulation and experiment to investigate the structure, thermodynamics and transport of three potential electrolytes, N-methyl-N-butylpyrrolidinium bis(trifluoromethylsufonyl)imide ([pyr14][TFSI]), N- methyl-N-propylpyrrolidinium bis(fluorosufonyl)imide ([pyr13][FSI]), and 1-ethyl-3-- methylimidazolium boron tetrafluoride ([EMIM][BF4]), as a function of Li (-) salt concentration and temperature. Structurally, Li(+) is shown to be solvated by three anion neighbors in [pyr14][TFSI] and four anion neighbors in both [pyr13][FSI] and [EMIM][BF4], and at all levels of xLi we find the presence of lithium aggregates. Furthermore, the computed density, diffusion, viscosity, and ionic conductivity show excellent agreement with experimental data. While the diffusion and viscosity exhibit a systematic decrease and increase, respectively, with increasing xLi, the contribution of Li(+) to ionic conductivity increases until reaching a saturation doping level of xLi 0.10. Comparatively, the Li(+) conductivity of [pyr14][TFSI] is an order of magnitude lower than that of the other liquids, which range between 0.1-0.3 mScm. The differences in Li(+) transport are reflected in the residence times of Li(+) with the anions, which are revealed to be much larger for [pyr14][TFSI] (up to 100 ns at the highest doping levels) than in either [EMIM][BF4] or [pyr13][FSI]. Finally, we comment on the relative kinetics of Li(+) transport in each liquid and we present strong evidence for transport through anion exchange (hopping) as opposed to the net motion of Li(+) with its solvation shell (vehicular).

molecular dynamics↗