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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 1,207 records · Page 67
All sourcesNASA NTRSDOE OSTI
DOE OSTI2016

Satellite detection of soil moisture related water stress impacts on ecosystem productivity using the MODIS-based photochemical reflectance index

We report satellite remote sensing provides continuous observations of vegetation properties that can be used to estimate global terrestrial ecosystem gross primary production (GPP). The Photochemical Reflectance Index (PRI) has been shown to be sensitive to vegetation photosynthetic light use efficiency (LUE), GPP and canopy water-stress. Here in this paper, we use the NASA EOS MODIS (Moderate Resolution Imaging Spectroradiometer) based PRI with eddy covariance CO2 flux measurements and meteorological observations from 20 tower sites representing major plant functional type (PFT) classes within the continental USA (CONUS) to assess GPP sensitivity to soil moisture related water stress. The sPRI (scaled PRI) metric derived using MODIS band 13 as a reference channel (sPRI13) shows generally higher correspondence with tower GPP estimates than other potential MODIS reference bands. The sPRI13 observations were used as a proxy for soil moisture related water supply constraints to LUE within a satellite data driven terrestrial carbon flux model to estimate GPP (GPPPRI). The GPPPRI calculations show generally favorable correspondence with tower GPP estimates (0.457 ≤ R2 ≤ 0.818), except for lower GPPPRI performance over evergreen needleleaf forest (ENF) sites. A regional model sensitivity analysis using the sPRI13 as a water supply proxy indicated that water restrictions limit GPP over more than 21% of the CONUS domain, particularly in drier climate areas where atmospheric moisture deficits (VPD) alone are insufficient to represent both atmosphere demand and water supply controls affecting productivity. Our results indicate strong potential of the MODIS sPRI13 to represent soil moisture related water supply controls influencing photosynthesis, with enhanced (1-km resolution) delineation of these processes closer to the scale of in situ tower observations. Lastly, these observations may provide an effective tool for characterizing sub-grid spatial heterogeneity in soil moisture related controls that inform coarser scale observations and estimates determined from other satellite observations and earth system models.

47 OTHER INSTRUMENTATION↗
DOE OSTI2021

Effect of electrode rinse solutions on the electrodialysis of concentrated salts

The data presented indicate that modest attention to the chemistry of the electrode rinse solution can yield as much as 56% improvement in process efficiency. When operating electrodialysis (ED) with salt concentrations greater than 10,000 mg/l (as NaCl) the amperage can be relatively high even at low voltages. To maximize the overall rate of ion transport from diluate to concentrate, there is a need to minimize resistances in the electrode cells since these can represent as much as 30% of the total resistances in the entire process and in this particular ED unit, represented resistance roughly equivalent to that within the membrane stack. This work describes the performance of a 10-cell pair, 200 cm 2 (0.02 m 2 ) per membrane, pilot ED unit operated in batch mode at 5 V potential. The feedstock to the stack was varied from 0.5% to 6% NaCl. Results from Volt-amp profiles (2.0–15 V) were used as the rationale for choosing the preferred electrode rinse solution, 90 g/l (kg/m 3 ) disodium sulfate at pH 12.5. The recommended solution of 30 g/l (kg/m 3 ) disodium sulfate at neutral pH was tested against stronger solutions (60, 90, and 120 g/l (kg/m 3 ) disodium sulfate) at neutral pH and with 1 g/l (kg/m 3 ) sodium hydroxide added to yield solutions at pH 12.5. There were stark differences in the performance of the ED unit between the solutions at pH 7 and those at pH 12.5. The slopes of the Volt-amp profiles improved indicating less resistance to ion flow at pH 12.5. Most of the difference can be attributed to the greater conductivity of sodium hydroxide compared to disodium sulfate, where even a modest addition of 1 g/l (kg/m 3 ) sodium hydroxide increased the conductivity of the solution between 8 and 20% depending on the concentration of disodium sulfate. Most notably, the initiation voltage was 2.39 ± 0.08 V with solutions at pH 7 and 1.99 V ± 0.04 V when the rinse solutions were around pH 12.5, a difference of around 0.42 V. Since the full batch runs were performed at 5.0 V, this 0.42 V differential represented a loss of 8% in process efficiency. A series of tests showed a shift in initiation voltage occurred between pH 11.5 and 12.5. Nernst equations for water electrolysis are coupled with a simple flux model that estimates the concentration of hydroxide and hydronium ions at the electrode surfaces. This model indicates that the potential demanded by the electrodes is directly linked to the current. Furthermore, there is a steep drop in the potential demanded by the anode when there is sufficient hydroxide available to generate oxygen from hydroxide as opposed to generation from water. The voltage demand is minimal at pH 12.5 and reflective of the reference standard voltage (just over 1.23 V predicted at 0.1 amps). However, the flux model predicts that the voltage demanded by the electrodes at pH 7 is 1.61 V at 0.1 amps (the lowest amperage measurable with the power pack). In conclusion, comparing this result to the reference standard (E 0 = -1.23 V) yields a satisfactory explanation for the observed difference below reference standard of 0.42 V.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Revising the dynamic energy budget theory with a new reserve mobilization rule and three example applications to bacterial growth

Dynamic energy budget (DEB) theory has been applied to model a wide range of organisms, including microbes. In the standard DEB model, biomass is partitioned into reserve and structural compartments, where reserve biomass is mobilized in a pseudolinear manner (while the reserve biomass density, defined as the ratio between reserve and structural biomass, decays linearly) to drive maintenance and the growth of structural biomass (and extracellular enzyme production if it is considered). However, the linear dynamics of the reserve biomass density makes the standard DEB model incapable of explaining the slowdown of microbial growth at high reserve density that is caused by macromolecular crowding effect which reduces biochemical reaction rates (a typical situation occurs when microbes are experiencing severe moisture stress) and is inconsistent with the observation that intracellular enzymatic reactions generally follow non-linear kinetics. By partitioning biomass into reserve, kinetic, and structural compartments, we show here that the Equilibrium Chemistry Approximation (ECA) kinetics can be used to represent enzymatically catalyzed reserve biomass mobilization that can then drive the kinetic and structural biomass synthesis. This revised DEB model better represents the tradeoff in ribosome allocation for structural growth and internal enzyme production, is structurally compatible with metabolic models of cell individuals, and includes the standard DEB model and the popular compromise model as special cases for representing population growth. We then applied the revised DEB model to interpret components of bacterial respiration, their dependence on substrate availability, and emergent microbial carbon use efficiency dynamics for an exponentially growing population. We found that the revised DEB model enables a better understanding of bacterial substrates use (carbon in our examples) than that can be derived from a few other models in the literature. In particular, the revised DEB model explains why carbon use efficiency may first increase, then plateau, and finally decrease with growth rate (and substrate uptake rate), as a function of proteomics. Additionally, the revised DEB model explains why the kinetic biomass compartment needs to be divided to reasonably incorporate proteomic control of microbial growth.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2012

Oral and inhaled corticosteroids: Differences in P-glycoprotein (ABCB1) mediated efflux

There is concern that P-glycoprotein mediated efflux contributes to steroid resistance. Therefore, this study examined bidirectional corticosteroid transport and induction capabilities for P-glycoprotein (P-gp) to understand which of the systemic and inhaled corticosteroids interacted with P-gp to the greatest extent. Hydrocortisone, prednisolone, prednisone, methylprednisolone, and dexamethasone represented systemically active drugs, while fluticasone propionate, beclomethasone dipropionate, ciclesonide and budesonide represented inhaled corticosteroids. Aldosterone and fludrocortisone represented mineralocorticoids. All drugs were detected using individually optimised HPLC protocols. Transport studies were conducted through Caco-2 monolayers. Hydrocortisone and aldosterone had efflux ratios below 1.5, while prednisone showed a P-gp mediated efflux ratio of only 1.8 compared to its active drug, prednisolone, with an efflux ratio of 4.5. Dexamethasone and beclomethasone had efflux ratios of 2.1 and 3.3 respectively, while this increased to 5.1 for methylprednisolone. Fluticasone showed an efflux ratio of 2.3. Protein expression studies suggested that all of the inhaled corticosteroids were able to induce P-gp expression, from 1.6 to 2 times control levels. Most of the systemic corticosteroids had higher passive permeability (> 20 × 10{sup −6} cm/s) compared to the inhaled corticosteroids (> 5 × 10{sup −6} cm/s), except for budesonide, with permeability similar to the systemic corticosteroids. Inhaled corticosteroids are not transported by P-gp to the same extent as systemic corticosteroids. However, they are able to induce P-gp production. Thus, inhaled corticosteroids may have greater interactions with other P-gp substrates, but P-gp itself is less likely to influence resistance to the drugs. -- Highlights: ► Inhaled corticosteroids are only weak substrates for P-gp, including budesonide. ► Inhaled corticosteroid potent P-gp inducers especially fluticasone and beclomethasone. ► Systemic corticosteroids are weak P-gp inducers. ► Mineralocorticoids not affected by P-gp mediated efflux.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2017

The monoamine oxidase inhibition properties of selected structural analogues of methylene blue

The thionine dye, methylene blue (MB), is a potent inhibitor of monoamine oxidase (MAO) A, a property that may, at least in part, mediate its antidepressant effects in humans and animals. The central inhibition of MAO-A by MB has also been linked to serotonin toxicity (ST) which may arise when MB is used in combination with serotonergic drugs. Structural analogues and the principal metabolite of MB, azure B, have also been reported to inhibit the MAO enzymes, with all compounds exhibiting specificity for the MAO-A isoform. To expand on the structure-activity relationships (SARs) of MAO inhibition by MB analogues, the present study investigates the human MAO inhibition properties of five MB analogues: neutral red, Nile blue, new methylene blue, cresyl violet and 1,9-dimethyl methylene blue. Similar to MB, these analogues also are specific MAO-A inhibitors with cresyl violet (IC{sub 50} = 0.0037 μM), Nile blue (IC{sub 50} = 0.0077 μM) and 1,9-dimethyl methylene blue (IC{sub 50} = 0.018 μM) exhibiting higher potency inhibition compared to MB (IC{sub 50} = 0.07 μM). Nile blue also represents a potent MAO-B inhibitor with an IC{sub 50} value of 0.012 μM. From the results it may be concluded that non-thionine MB analogues (e.g. cresyl violet and Nile blue) also may exhibit potent MAO inhibition, a property which should be considered when using these compounds in pharmacological studies. Benzophenoxazines such as cresyl violet and Nile blue are, similar to phenothiazines (e.g. MB), representative of high potency MAO-A inhibitors with a potential risk of ST. - Highlights: • MB analogues, cresyl violet and Nile blue, are high potency MAO-A inhibitors. • Nile blue also represents a potent MAO-B inhibitor. • Potent MAO-A inhibition should alert to potential serotonin toxicity.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2017

Toxicological characterisation of two novel selective aryl hydrocarbon receptor modulators in Sprague-Dawley rats

The aryl hydrocarbon receptor (AHR) mediates the toxicity of dioxins, but also plays important physiological roles. Selective AHR modulators, which elicit some effects imparted by this receptor without causing the marked toxicity of dioxins, are presently under intense scrutiny. Two novel such compounds are IMA-08401 (N-acetyl-N-phenyl-4-acetoxy-5-chloro-1, 2-dihydro-1-methyl-2-oxo-quinoline-3-carboxamide) and IMA-07101 (N-acetyl-N-(4-trifluoromethylphenyl)-4-acetoxy-1, 2-dihydro-5-methoxy-1-methyl-2-oxo-quinoline-3-carboxamide). They represent, as diacetyl prodrugs, AHR-active metabolites of the drug compounds laquinimod and tasquinimod, respectively, which are intended for the treatment of autoimmune diseases and cancer. Here, we toxicologically assessed the novel compounds in Sprague-Dawley rats, after a single dose (8.75–92.5 mg/kg) and 5-day repeated dosing at the highest doses achievable (IMA-08401: 100 mg/kg/day; and IMA-07101: 75 mg/kg/day). There were no overt clinical signs of toxicity, but body weight gain was marginally retarded, and the treatments induced minimal hepatic extramedullary haematopoiesis. Further, both the absolute and relative weights of the thymus were significantly decreased. Cyp1a1 gene expression was substantially increased in all tissues examined. The hepatic induction profile of other AHR battery genes was distinct from that caused by 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD). The only marked alterations in serum clinical chemistry variables were a reduction in triglycerides and an increase in 3-hydroxybutyrate. Liver and kidney retinol and retinyl palmitate concentrations were affected largely in the same manner as reported for TCDD. In vitro, the novel compounds activated CYP1A1 effectively in H4IIE cells. Altogether, these novel compounds appear to act as potent activators of the AHR, but lack some major characteristic toxicities of dioxins. They therefore represent promising new selective AHR modulators. - Highlights: • IMA-08401 and IMA-07101 are novel, effective activators of the AHR. • In rats, they lacked the wasting syndrome and thyroid imbalance typical of TCDD. • They also affected the AHR-battery genes in a distinct manner. • Therefore, the compounds appear to represent promising new selective AHR modulators. • They may have potential as drug compound candidates and research tools.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2011

Evaluation of methane emissions from Palermo municipal landfill: Comparison between field measurements and models

Methane (CH{sub 4}) diffuse emissions from Municipal Solid Waste (MSW) landfills represent one of the most important anthropogenic sources of greenhouse gas. CH{sub 4} is produced by anaerobic biodegradation of organic matter in landfilled MSW and constitutes a major component of landfill gas (LFG). Gas recovery is a suitable method to effectively control CH{sub 4} emissions from landfill sites and the quantification of CH{sub 4} emissions represents a good tool to evaluate the effectiveness of a gas recovery system in reducing LFG emissions. In particular, LFG emissions can indirectly be evaluated from mass balance equations between LFG production, recovery and oxidation in the landfill, as well as by a direct approach based on LFG emission measurements from the landfill surface. However, up to now few direct measurements of landfill CH{sub 4} diffuse emissions have been reported in the technical literature. In the present study, both modeling and direct emission measuring methodologies have been applied to the case study of Bellolampo landfill located in Palermo, Italy. The main aim of the present study was to evaluate CH{sub 4} diffuse emissions, based on direct measurements carried out with the flux accumulation chamber (static, non-stationary) method, as well as to obtain the CH{sub 4} contoured flux map of the landfill. Such emissions were compared with the estimate achieved by means of CH{sub 4} mass balance equations. The results showed that the emissions obtained by applying the flux chamber method are in good agreement with the ones derived by the application of the mass balance equation, and that the evaluated contoured flux maps represent a reliable tool to locate areas with abnormal emissions in order to optimize the gas recovery system efficiency.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2015

Cross-current leaching of indium from end-of-life LCD panels

Graphical abstract: Display Omitted - Highlights: • End-of-life LCD panels represent a source of indium. • Several experimental conditions for indium leaching have been assessed. • Indium is completely extracted with 2 M sulfuric acid at 80 °C for 10 min. • Cross-current leaching improves indium extraction and operating costs are lowered. • Benefits to the environment come from reduction of CO{sub 2} emissions and reagents use. - Abstract: Indium is a critical element mainly produced as a by-product of zinc mining, and it is largely used in the production process of liquid crystal display (LCD) panels. End-of-life LCDs represent a possible source of indium in the field of urban mining. In the present paper, we apply, for the first time, cross-current leaching to mobilize indium from end-of-life LCD panels. We carried out a series of treatments to leach indium. The best leaching conditions for indium were 2 M sulfuric acid at 80 °C for 10 min, which allowed us to completely mobilize indium. Taking into account the low content of indium in end-of-life LCDs, of about 100 ppm, a single step of leaching is not cost-effective. We tested 6 steps of cross-current leaching: in the first step indium leaching was complete, whereas in the second step it was in the range of 85–90%, and with 6 steps it was about 50–55%. Indium concentration in the leachate was about 35 mg/L after the first step of leaching, almost 2-fold at the second step and about 3-fold at the fifth step. Then, we hypothesized to scale up the process of cross-current leaching up to 10 steps, followed by cementation with zinc to recover indium. In this simulation, the process of indium recovery was advantageous from an economic and environmental point of view. Indeed, cross-current leaching allowed to concentrate indium, save reagents, and reduce the emission of CO{sub 2} (with 10 steps we assessed that the emission of about 90 kg CO{sub 2}-Eq. could be avoided) thanks to the recovery of indium. This new strategy represents a useful approach for secondary production of indium from waste LCD panels.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2015

Coupling scales for modelling heavy metal vaporization from municipal solid waste incineration in a fluid bed by CFD

Highlights: • A CFD two-scale model is formulated to simulate heavy metal vaporization from waste incineration in fluidized beds. • MSW particle is modelled with the macroscopic particle model. • Influence of bed dynamics on HM vaporization is included. • CFD predicted results agree well with experimental data reported in literature. • This approach may be helpful for fluidized bed reactor modelling purposes. - Abstract: Municipal Solid Waste Incineration (MSWI) in fluidized bed is a very interesting technology mainly due to high combustion efficiency, great flexibility for treating several types of waste fuels and reduction in pollutants emitted with the flue gas. However, there is a great concern with respect to the fate of heavy metals (HM) contained in MSW and their environmental impact. In this study, a coupled two-scale CFD model was developed for MSWI in a bubbling fluidized bed. It presents an original scheme that combines a single particle model and a global fluidized bed model in order to represent the HM vaporization during MSW combustion. Two of the most representative HM (Cd and Pb) with bed temperatures ranging between 923 and 1073 K have been considered. This new approach uses ANSYS FLUENT 14.0 as the modelling platform for the simulations along with a complete set of self-developed user-defined functions (UDFs). The simulation results are compared to the experimental data obtained previously by the research group in a lab-scale fluid bed incinerator. The comparison indicates that the proposed CFD model predicts well the evolution of the HM release for the bed temperatures analyzed. It shows that both bed temperature and bed dynamics have influence on the HM vaporization rate. It can be concluded that CFD is a rigorous tool that provides valuable information about HM vaporization and that the original two-scale simulation scheme adopted allows to better represent the actual particle behavior in a fluid bed incinerator.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2019

Filtered lifting line theory and application to the actuator line model

Lifting line theory describes the cumulative effect of shed vorticity from finite span lifting surfaces. In this work, the theory is reformulated to improve the accuracy of the actuator line model (ALM). This model is a computational tool used to represent lifting surfaces, such as wind-turbine blades in computational fluid dynamics. In ALM, blade segments are represented by means of a Gaussian body force distribution with a prescribed kernel size. Prior analysis has shown that a representation of the blade using an optimal kernel width $\unicode[STIX]{x1D716}^{opt}$ of approximately one quarter of the chord size results in accurate predictions of the velocity field and loads along the blades. Also, simulations have shown that use of the optimal kernel size yields accurate representation of the tip-vortex size and the associated downwash resulting in accurate predictions of the tip losses. In this work, we address the issue of how to represent the effects of finite span wings and tip vortices when using Gaussian body forces with a kernel size larger than the optimal value. This question is relevant in the context of coarse-scale large-eddy simulations that cannot afford the fine resolutions required to resolve the optimal kernel size. For this purpose, we present a filtered lifting line theory for a Gaussian force distribution. Based on the streamwise component of the vorticity transport equation, we develop an analytical model for the induced velocity resulting from the spanwise changes in lift force for an arbitrary kernel scale. The results are used to derive a subfilter-scale velocity model that is used to correct the velocity along the blade when using kernel sizes larger than $\unicode[STIX]{x1D716}^{opt}$ . Tests are performed in large-eddy simulation of flow over fixed wings with constant and elliptic chord distributions using various kernel sizes. Results show that by using the proposed subfilter velocity model, kernel-size independent predictions of lift coefficient and total lift forces agree with those obtained with the optimal kernel size.

17 WIND ENERGY↗
DOE OSTI2024

Stochastic modal velocity field in rough-wall turbulence

Stochastically generated instantaneous velocity profiles are used to reproduce the outer region of rough-wall turbulent boundary layers in a range of Reynolds numbers extending from the wind tunnel to field conditions. Each profile consists in a sequence of steps, defined by the modal velocities and representing uniform momentum zones (UMZs), separated by velocity jumps representing the internal shear layers. Height-dependent UMZ is described by a minimal set of attributes: thickness, mid-height elevation, and streamwise (modal) and vertical velocities. These are informed by experimental observations and reproducing the statistical behaviour of rough-wall turbulence and attached eddy scaling, consistent with the corresponding experimental datasets. Sets of independently generated profiles are reorganized in the streamwise direction to form a spatially consistent modal velocity field, starting from any randomly selected profile. The operation allows one to stretch or compress the velocity field in space, increases the size of the domain and adjusts the size of the largest emerging structures to the Reynolds number of the simulated flow. By imposing the autocorrelation function of the modal velocity field to be anchored on the experimental measurements, we obtain a physically based spatial resolution, which is employed in the computation of the velocity spectrum, and second-order structure functions. The results reproduce the Kolmogorov inertial range extending from the UMZ and their attached-eddy vertical organization to the very-large-scale motions (VLSMs) introduced with the reordering process. The dynamic role of VLSM is confirmed in the –u'w' co-spectra and in their vertical derivative, representing a scale-dependent pressure gradient contribution.

42 ENGINEERING↗
DOE OSTI2018

From the Nonexistent Polar Intermetallic Pt 3 Pr 4 via Pt 2– x Pr 3 to Pt/Sn/Pr Ternaries

Here the Pt–Pr phase diagram has been explored well, recent work on rare-earth metal cluster halides with endohedral transition metal atoms has provided a new binary intermetallic that is nonexistent in the known phase diagram: The binary Pt 3 Pr 4 ( 1 ) crystallizes in a new structure type ( mP 56, P 2 1 /c, a = 12.353(2) Å, b = 7.4837(9) Å, c = 17.279(2) Å, β = 118.003(7)°, Z = 8) with six crystallographically independent Pt as well as eight Pr positions. The subsequent detailed investigation has led to another previously unreported, binary phase with the Ga 2 Gd 3 structure type, Pt 2–x Pr 3 ( 2 , tI 80, I 4/ mcm , a = 11.931(9) Å, c = 14.45(1) Å, Z = 16), that is practically overlapping with the rhombohedral Pt 2 Pr 3 existing in the phase diagram. Application of different tin containing fluxes to reproduce the newly detected phases brought about two almost iso-compositional ternary compounds with Sn, Pt 4 Sn 6 Pr 2.91 ( 3 ), and Pt 4 Sn 6 Pr 3 ( 4 ), as well as Pt 12 Sn 24 Pr 4.84 ( 5 ). 3 is a representative of the Pt 4 Ge 6 Ce 3 type ( oP 52, Pnma , a = 7.2863(3) Å, b = 4.4909(2) Å, c = 35.114(2) Å), while 4 represents a new variant of the prolific T 4 E 6 R 3 family (T = transition metal, E = main group (semi)metal, R = rare-earth metal; Pt 4 Sn 6 Pr 3 : oP 52, Pnma , a = 27.623(1) Å, b = 4.5958(2) Å, c = 9.3499(5) Å). Pt 12 Sn 24 Pr 5–x ( 5 ) crystallizes as a variant of the Ni 8 Sn 16 Gd 3 type ( cI 82, Im $\bar{3}$, a = 12.274(1) Å, Z = 2). Electronic structure calculations provide hints on the origin of the structural changes (pseudo-polymorphism) for Pt x Pr 3 with x = 1.97 and 2.00, respectively, and reveal that heteroatomic Pt–Pr bonding strongly dominates in both binaries while the addition of the reactive metal tin leads to dominating Pt–Sn bonding interactions in the ternaries; Pt–Pt bonding interactions are strong but represent a minority in the binaries and are not present at all in the ternaries.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Configurational-Bias Monte Carlo Back-Mapping Algorithm for Efficient and Rapid Conversion of Coarse-Grained Water Structures into Atomistic Models

Coarse-grained molecular dynamics (MD) simulations represent a powerful approach to simulate longer time scale and larger length scale phenomena than those accessible to all-atom models. The gain in efficiency, however, comes at the cost of atomistic details. The reverse transformation, also known as back-mapping, of coarse grained beads into their atomistic constituents represents a major challenge. Most existing approaches are limited to specific molecules or specific force-fields and often rely on running a long time atomistic MD of the back-mapped configuration to arrive at an optimal solution. Such approaches are problematic when dealing with systems with high diffusion barriers. Here, we introduce a new extension of the configurational-bias-Monte-Carlo (CBMC) algorithm, which we term the crystalline-configurational-bias-Monte-Carlo (C-CBMC) algortihm, that allows rapid and efficient conversion of a coarse-grained model back into its atomistic representation. Although the method is generic, we use a coarse-grained water model as a representative example and demonstrate the back-mapping or reverse transformation for model systems ranging from the ice-liquid water interface to amorphous and crystalline ice configurations. A series of simulations using the TIP4P/Ice model are performed to compare the new CBMC method to several other standard Monte Carlo and Molecular Dynamics based back-mapping techniques. In all the cases, the C-CBMC algorithm is able to find optimal hydrogen bonded configuration many thousand evaluations/steps sooner than the other methods compared within this paper. For crystalline ice structures such as a hexagonal, cubic, and cubic-hexagonal stacking disorder structures, the C-CBMC was able to find structures that were between 0.05 and 0.1 eV/water molecule lower in energy than the ground state energies predicted by the other methods. Detailed analysis of the atomistic structures show a significantly better global hydrogen positioning when contrasted with the existing simpler back-mapping methods. The error in the RDFs of backmapped relative to reference configuration for the CCBMC, MD, and MC were found to be 6.9, 8.7, and 12.9 respectively for the hexagonal system. For the cubic system the relative error of the RDFs for the CCBMC, MD, and MC were found to be 18.2, 34.6, and 39.0 respectively. Finally, our results demonstrate the efficiency and efficacy of our new back-mapping approach, especially for crystalline systems where simple force-field based relaxations have a tendency to get trapped in local minima.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2016

Diffusion of biomass pyrolysis products in H-ZSM-5 by molecular dynamics simulations

Diffusion of biomass pyrolysis vapors and their upgraded products is an essential catalytic property of zeolites during catalytic fast pyrolysis and likely plays a critical role in the selectivity of these catalysts. Characterizing the diffusivities of representative biofuel molecules is critical to understand shape selectivity and interpret product distribution. Yet, experimental measurements on the diffusivities of oxygenated biofuel molecules at pyrolysis temperatures are very limited in the literature. As an alternative approach, we conducted MD simulations to measure the diffusion coefficients of several selected molecules that are representative of biomass pyrolysis vapors, namely water, methanol, glycolaldehyde, and toluene in H-ZSM-5 zeolite. The results show the diffusion coefficients calculated via MD simulations are consistent with available NMR measurements at room temperature. The effect of molecular weight and molecular critical diameter on the diffusivity among the chosen model compounds is also examined. Furthermore, we have characterized the diffusivities of representative biofuel molecules, namely xylene isomers, in H-ZSM-5. Our calculations determined that the ratio of the diffusion coefficients for xylene isomers is p -xylene: o -xylene: m -xylene ≈ 83:3:1 at 700 K. Furthermore, our results also demonstrate the different diffusivity between p-xylene and toluene is due to the molecular orientations when the molecules diffuse along the channels in H-ZSM-5 and provide deep insight into the effect of molecular orientation on its diffusivity.

09 BIOMASS FUELS↗
DOE OSTI2026

Ultrafast population and structural dynamics of a Ni-bipyridine photoredox catalyst reveal a significant deactivation pathway

The ultrafast excited state pathways and dynamics of NiII-bipyridine complexes influence the yield of photochemical processes involved in their catalytic cross-coupling reactions. Here we present ultrafast Ni K x-ray emission spectroscopy (XES) and x-ray solution scattering (XSS) of a NiII-bipyridine aryl halide complex, [Ni(t-Bubpy)(o-tol)Br], to quantify the excited state population dynamics and structural changes of the pre-catalyst. Due to the local spin-sensitivity of XES, the population dynamics of metal-to-ligand charge transfer (MLCT) and metal-centered (MC) excited states is established. A rapid ground state recovery pathway is newly identified, representing a significant deactivation pathway during photocatalysis. Furthermore, the pseudotetrahedral structure of the long-lived MC excited state is unambiguously identified and refined by XSS. The results advance our understanding of the ultrafast relaxation mechanisms that impact the photocatalytic mechanism and yield for NiII-bipyridine aryl halide cross-coupling catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Degradation Mechanisms of Magnesium Metal Anodes in Electrolytes Based on (CF 3 SO 2 ) 2 N – at High Current Densities

The energy density of rechargeable batteries utilizing metals as anodes surpasses that of Li ion batteries, which employ carbon instead. Among possible metals, magnesium represents a potential alternative to the conventional choice, lithium, in terms of storage density, safety,stability, and cost. However, a major obstacle for metal-based batteries is the identification of electrolytes that show reversible deposition/dissolution of the metal anode and support reversible intercalation of ions into a cathode. Traditional Grignard-based Mg electrolytes are excellent with respect to the reversible deposition of Mg, but their limited anodic stability and compatibility with oxide cathodes hinder their applicability in Mg batteries with higher voltage. Non-Grignard electrolytes, which consist of ethereal solutions of magnesium(II) bis(trifluoromethanesulfonyl)imide (Mg(TFSI) 2 ), remain fairly stable near the potential of Mg deposition. The slight reactivity of these electrolytes toward Mg metal can be remedied by the addition of surface-protecting agents, such as MgCl 2 . Hence, ethereal solutions of Mg(TFSI) 2 salt with MgCl 2 as an additive have been suggested as a representative non-Grignard Mg electrolyte. In this work, the degradation mechanisms of a Mg metal anode in the TFSI-based electrolyte were studied using a current density of 1 mA cm -2 and an areal capacity of ~0.4 mAh cm -2 , which is close to those used in practical applications. The degradation mechanisms identified include the corrosion of Mg metal, which causes the loss of electronic pathways and mechanical integrity, the nonuniform deposition of Mg, and the decomposition of TFSI - anions. This study not only represents an assessment of the behavior of Mg metal anodes at practical current density and areal capacity but also details the outcomes of interfacial passivation, which was detected by simple cyclic voltammetry experiments. This study also points out the absolute absence of any passivation at the electrode-electrolyte interface for the premise of developing electrolytes compatible with a metal anode.

25 ENERGY STORAGE↗
DOE OSTI2024

Chemical Differences between Phenolic Secondary Organic Aerosol Formed through Gas-Phase and Aqueous-Phase Reactions

Phenolic compounds, which are significant emissions from biomass burning (BB), undergo rapid photochemical reactions in both gas and aqueous phases to form secondary organic aerosol, namely, gasSOA and aqSOA, respectively. The formation of gasSOA and aqSOA involves different reaction mechanisms, leading to different product distributions. In this study, we investigate the gaseous and aqueous reactions of guaiacol a representative BB phenol to elucidate the compositional differences between phenolic aqSOA and gasSOA. Aqueous-phase reactions of guaiacol produce higher SOA yields than gas-phase reactions (e.g., roughly 60 vs 30% at one half-life of guaiacol). These aqueous reactions involve more complex reaction mechanisms and exhibit a more gradual SOA evolution than their gaseous counterparts. Initially, gasSOA forms with high oxidation levels (O/C > 0.82), while aqSOA starts with lower O/C (0.55–0.75). However, prolonged aqueous-phase reactions substantially increase the oxidation state of aqSOA, making its bulk chemical composition closer to that of gasSOA. Additionally, aqueous reactions form a greater abundance of oligomers and high-molecular-weight compounds, alongside a more sustained production of carboxylic acids. AMS spectral signatures representative of phenolic gasSOA have been identified, which, together with tracer ions of aqSOA, can aid in the interpretation of field observation data on aerosol aging within BB smoke. The notable chemical differences between phenolic gasSOA and aqSOA highlighted in this study also underscore the importance of accurately representing both pathways in atmospheric models to better predict the aerosol properties and their environmental impacts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Mysterious SiB 3 : Identifying the Relation between α- and β-SiB 3

Binary silicon boride SiB 3 has been reported to occur in two forms, as disordered and nonstoichiometric α-SiB 3–x , which relates to the α-rhombohedral phase of boron, and as strictly ordered and stoichiometric β-SiB 3 . Similar to other boron-rich icosahedral solids, these SiB 3 phases represent potentially interesting refractory materials. However, their thermal stability, formation conditions, and thermodynamic relation are poorly understood. Here, we map the formation conditions of α-SiB 3–x and β-SiB 3 and analyze their relative thermodynamic stabilities. α-SiB 3–x is metastable (with respect to β-SiB 3 and Si), and its formation is kinetically driven. Pure polycrystalline bulk samples may be obtained within hours when heating stoichiometric mixtures of elemental silicon and boron at temperatures 1200–1300 °C. At the same time, α-SiB 3–x decomposes into SiB6 and Si, and optimum time-temperature synthesis conditions represent a trade-off between rates of formation and decomposition. The formation of stable β-SiB 3 was observed after prolonged treatment (days to weeks) of elemental mixtures with ratios Si/B = 1:1–1:4 at temperatures 1175–1200 °C. The application of high pressures greatly improves the kinetics of SiB 3 formation and allows decoupling of SiB 3 formation from decomposition. Quantitative formation of β-SiB 3 was seen at 1100 °C for samples pressurized to 5.5–8 GPa. β-SiB 3 decomposes peritectoidally at temperatures between 1250 and 1300 °C. The highly ordered nature of β-SiB 3 is reflected in its Raman spectrum, which features narrow and distinct lines. In contrast, the Raman spectrum of α-SiB 3–x is characterized by broad bands, which show a clear relation to the vibrational modes of isostructural, ordered B 6 P. The detailed composition and structural properties of disordered α-SiB 3–x were ascertained by a combination of single-crystal X-ray diffraction and 29 Si magic angle spinning NMR experiments. Notably, the compositions of polycrystalline bulk samples (obtained at T ≤ 1200 °C) and single crystal samples (obtained from Si-rich molten Si–B mixtures at T > 1400 °C) are different, SiB 2.93(7) and SiB 2.64(2) , respectively. The incorporation of Si in the polar position of B 12 icosahedra results in highly strained cluster units. This disorder feature was accounted for in the refined crystal structure model by splitting the polar position into three sites. The electron-precise composition of α-SiB 3–x is SiB 2.5 and corresponds to the incorporation of, on average, two Si atoms in each B 12 icosahedron. Accordingly, α-SiB 3–x constitutes a mixture of B 10 Si 2 and B 11 Si clusters. The structural and phase stability of α-SiB 3–x were explored using a first-principles cluster expansion. The most stable composition at 0 K is SiB 2.5 , which however is unstable with respect to the decomposition β-SiB 3 + Si. Modeling of the configurational and vibrational entropies suggests that α-SiB 3–x only becomes more stable than β-SiB 3 at temperatures above its decomposition into SiB 6 and Si. Hence, we conclude that α-SiB 3–x is metastable at all temperatures. Density functional theory electronic structure calculations yield band gaps of similar size for electron-precise α-SiB 2.5 and β-SiB 3 , whereas α-SiB 3 represents a p-type conductor.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗