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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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All sourcesNASA NTRSDOE OSTI
NASA NTRS2007

Calculational and Experimental Investigations of the Pressure Effects on Radical - Radical Cross Combinations Reactions: C2H5 + C2H3

Pressure-dependent product yields have been experimentally determined for the cross-radical reaction C2H5 + C2H3. These results have been extended by calculations. It is shown that the chemically activated combination adduct, 1-C4H8*, is either stabilized by bimolecular collisions or subject to a variety of unimolecular reactions including cyclizations and decompositions. Therefore the "apparent" combination/disproportionation ratio exhibits a complex pressure dependence. The experimental studies were performed at 298 K and at selected pressures between about 4 Torr (0.5 kPa) and 760 Torr (101 kPa). Ethyl and vinyl radicals were simultaneously produced by 193 nm excimer laser photolysis of C2H5COC2H3 or photolysis of C2H3Br and C2H5COC2H5. Gas chromatograph/mass spectrometry/flame ionization detection (GC/MS/FID) were used to identify and quantify the final reaction products. The major combination reactions at pressures between 500 (66.5 kPa) and 760 Torr are (1c) C2H5 + C2H3 yields 1-butene, (2c) C2H5 + C2H5 yields n-butane, and (3c) C2H3 + C2H3 yields 1,3-butadiene. The major products of the disproportionation reactions are ethane, ethylene, and acetylene. At moderate and lower pressures, secondary products, including propene, propane, isobutene, 2-butene (cis and trans), 1-pentene, 1,4-pentadiene, and 1,5-hexadiene are also observed. Two isomers of C4H6, cyclobutene and/or 1,2-butadiene, were also among the likely products. The pressure-dependent yield of the cross-combination product, 1-butene, was compared to the yield of n-butane, the combination product of reaction (2c), which was found to be independent of pressure over the range of this study. The [ 1-C4H8]/[C4H10] ratio was reduced from approx.1.2 at 760 Torr (101 kPa) to approx.0.5 at 100 Torr (13.3 kPa) and approx.0.1 at pressures lower than about 5 Torr (approx.0.7 kPa). Electronic structure and RRKM calculations were used to simulate both unimolecular and bimolecular processes. The relative importance of C-C and C-H bond ruptures, cyclization, decyclization, and complex decompositions are discussed in terms of energetics and structural properties. The pressure dependence of the product yields were computed and dominant reaction paths in this chemically activated system were determined. Both modeling and experiment suggest that the observed pressure dependence of [1-C4H8]/[C4H10] is due to decomposition of the chemically activated combination adduct 1-C4H8* in which the weaker allylic C-C bond is broken: H2C=CHCH2CH3 yields C3H5 + CH3. This reaction occurs even at moderate pressures of approx.200 Torr (26 kPa) and becomes more significant at lower pressures. The additional products detected at lower pressures are formed from secondary radical-radical reactions involving allyl, methyl, ethyl, and vinyl radicals. The modeling studies have extended the predictions of product distributions to different temperatures (200-700 K) and a wider range of pressures (10(exp -3) - 10(exp 5) Torr). These calculations indicate that the high-pressure [1-C4H8]/[C4H10] yield ratio is 1.3 +/- 0.1.

Fahr, Askar↗
DOE OSTI2023

Re-Examination of the N 2 O + O Reaction

The reaction of N 2 O with O is a key step in consumption of nitrous oxide in thermal processes. It has two product channels, NO + NO (R2) and N 2 + O 2 (R3). The rate constant for R2 has been measured both in the forward and the reverse direction at elevated temperature and is well established. However, the rate constant for the N 2 + O 2 channel (R3) has been difficult to quantify and has significant error limits. Here, the direct reaction on the triplet surface has a barrier of around 40 kcal mol –1 , and it is too slow for the N 2 + O 2 channel to have any practical significance. Recently, Pham and Lin (2022) suggested an alternative low activation energy reaction path that involves intersystem crossing and reaction on the singlet surface. In the present work, we re-examined a wide range of experiments relevant for the N 2 O + O reaction through kinetic modeling, paying attention to the impact of artifacts such as impurities and surface reactions. Experimental results from shock tubes and batch reactors on the final NO yield in N 2 O decomposition, covering temperatures of 973–2200 K and pressures of 0.013–11.5 atm, support k 3 ~ 0, consistent with the high activation energy for reaction on the triplet surface and a low probability of ISC.

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

Updates on Nucleon Form Factors from Clover-on-HISQ Lattice Formulation

Updates on results for the electric, magnetic and axial vector form factors are presented. The data analyzed cover high statistics measurements on 11 ensembles generated with 2+1+1 flavors of HISQ fermions by the MILC collaboration. The data cover the range 0.05 fm < a < 0.15 fm in lattice spacing, 135 MeV < M π < 320 MeV in the pion mass and 3.3 < M π L < 5.5 in the lattice size. Fits to control excited-state contamination use up to 3-states in the spectral decomposition of the 3-point functions. The simultaneous chiral-continuum-finite-volume fits include leading order corrections in each of the three variables.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
NASA NTRS2000

Kinetics of the Cl(2)P(J)) + CH4 Reaction: Effects of Secondary Chemistry Below 300 K

Absolute rate data for the Cl(2)P(J) + CH4 yields HCl + CH3 reaction have been obtained from 218 to 298 K by using the discharge-flow resonance fluorescence technique at I Torr total pressure. The result at 298 K is (10.1 +/- 0.6) x 10(exp -14) cu cm/molecule/s. The temperature dependence in Arrhenius form is (6.5 +/- 0.9 ) x 10(exp -12) exp[(-1235 +/- 34 )/T]. The errors given are one standard deviation; overall experimental error is estimated at +/- 15%. Because of the relatively large disagreement among earlier measurements at low temperatures, the results were examined for possible effects of non-Boltzmann spin distribution and vibrational excitation of CH4, secondary chemistry of CH3 radicals, and impurities in the CH4 source. There was no significant change in the observed rate constant when an efficient spin quencher, CF4, was added and estimates indicate that vibrational partitioning in CH4 should be at the ambient reactor temperature before the start of the reaction. The results were also independent of the source of Cl atoms (microwave discharge or thermal decomposition of Cl2) and whether CH4 was purified in-situ. However, the observed rate constant did depend on initial Cl atom concentrations and to a lesser extent on CH4 concentrations. Numerical simulations were used to assess the importance of secondary chemistry over a range of reactant concentrations

Wang, J. J.↗
NASA NTRS2011

Correlation of LEND and Diviner Data

Correlated results from the Lunar Reconnaissance Orbiter's (LRO) Lunar Exploration Neutron Detector (LEND) and Lunar Orbiting Laser Altimeter (LOLA) suggest insolation effects influence the spatial distribution of Lunar H poleward of 60deg latitude. Diviner results indicate an insolation induced thermal contrast between pole-facing and equator-facing slopes of crater walls. Our research shows that the contrasting thermal conditions observed in pole-facing vs equator-facing slopes and epithermal neutron rates from LEND are positively correlated. Numerical transformations of LOLA topography facilitated a systematic decomposition of LEND epithermal maps as a function of insolation effects. The results suggest a significantly positive local epithermal contrast in these regions. Comparing pole-facing and equator-facing slopes, we find that the pole-facing slopes show epithermal neutron suppression ranging from -0.005 to 0.02 cps relative to the equator-facing slopes .. We further investigate insolation effects on epithermal neutrons by comparing the predicted insolation contrast derived from the 3-D LOLA topography model with the LEND results. We also investigate and discuss the possibility of slope mass wasting effects being correlated with our insolation-effect hypothesis

McClanahan, Tim↗
DOE OSTI2018

Thermodynamic modeling of the deposition of Si—C—N films from the gas phase during the decomposition of organosilicon compounds

Thermodynamic modeling of the process of chemical vapor deposition (CVD) of SiC{sub x} and SiC{sub x}N{sub y} films from the gas phase was carried out using organosilicon compounds (EtN(SiMe{sub 3}){sub 2}, PhN(SiMe{sub 3}){sub 2}, and PhSiMe{sub 3}) at reactor pressures of 0.01 and 10 Torr in the temperature range of 500–1200 K. It was established that regions of existence of two phase complexes, namely, SiC + Si{sub 3}N{sub 4} + C and SiC + C, were present on the CVD diagrams calculated for the EtN(SiMe{sub 3}){sub 2}—He and PhN(SiMe{sub 3}){sub 2}—He systems. The CVD diagrams calculated for the EtN(SiMe{sub 3}){sub 2}—NH{sub 3}, PhN(SiMe{sub 3}){sub 2}—NH{sub 3}, and PhSiMe{sub 3}—NH{sub 3} systems have regions of existence of three phase complexes, namely, Si{sub 3}N{sub 4} + C, SiC + Si{sub 3}N{sub 4} + C, and SiC + C. The composition of the obtained silicon-containing films was calculated.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2020

In Situ Studies of Methanol Decomposition Over Cu(111) and Cu2O/Cu(111): Effects of Reactant Pressure, Surface Morphology, and Hot Spots of Active Sites

The dissociative adsorption of methanol was investigated on Cu(111) and ultrathin Cu 2 O films. We employed synchrotron-based Ambient Pressure X-ray Photoelectron Spectroscopy (AP-XPS) and Scanning Tunneling Microscopy (STM) to study the dynamics of gas–solid interactions, and calculations based on Density Functional Theory (DFT) were used to examine the reaction path. C 1s XPS spectra revealed that methanol underwent dissociative adsorption on plain Cu(111) to form methoxy (CH 3 O), formaldehyde (H 2 CO), and formate (HCOO) at a pressure range of 0.5–10 mTorr, with these species remaining on the surface after evacuation. This was accompanied by the appearance of a low coverage (~0.05 ML) of O ads in the O 1s which can be considered a highly active site for methanol activation. The high activity is apparent by a coverage of 0.8 ML of methoxy at room temperature. STM was unable to image these species at room temperature as they were highly mobile on metallic copper. In contrast, for CH 3 OH on Cu 2 O/Cu(111), STM showed clear hot spots for reaction and a complex array of adsorption structures. On the oxide substrate, there was decomposition of methanol to H 2 CO, CH 3 O, HCOO, and hydrocarbon species (CH x ) due to the subsequent interactions of methanol with lattice oxygen. Cu(111) remained entirely saturated with decomposition products under 10 mTorr of methanol (θ ≈ 0.97 ML), whereas the Cu 2 O overlayer was saturated at a much lower coverage (θ ≈ 0.30 ML). STM revealed rows and step edges of Cu 2 O decorated with decomposition products and metallic Cu islands ~5 nm in size. The difference in activity between Cu(111) and Cu 2 O/Cu(111) is attributed to the significant amount of O present on the oxide surface. Additionally, Density Functional theory (DFT) calculations described the XPS measurements well, showing a likely methanol dissociation to *CH 3 O and therefore a surface reduction. More importantly, the DFT results revealed that it was the chemisorbed oxygen on Cu 2 O/Cu(111) which oxidized the dissociated *CH 3 O to *HCOO and eventually CO 2 , while the reaction only involving upper oxygen on the Cu 2 O hexagonal ring led to the formation of H 2 CO.

36 MATERIALS SCIENCE↗
DOE OSTI2014

Extracting physics through deep data analysis

In recent decades humankind has become very apt at generating and recording enormous amounts of data, ranging from tweets and selfies on social networks, to financial transactions in banks and stores. The scientific community has not shunned this popular trend and now routinely produces hundreds of petabytes of data per year [1]. This is because materials and phenomena in the world around us exist in an interweaved, entangled form, which gives rise to the complexity of the Universe and determines the size and complexity of the data that describes it. Science and technology endeavor to unravel this convolution and extract pure components from the mixtures, be it in ore mining and metal smelting or separation of thermal conductivity into the electronic and phononic contributions. Decomposition of complex behavior is the key to understanding manifestations of Nature. However, tools to carry out this task are not readily available, and therefore, intricate systems often remain well-characterized experimentally, but still not well understood due to intricacy of the collected data. Lastly, in materials science, understanding and ultimately designing new materials with complex properties will require the ability to integrate and analyze data from multiple instruments, including computational models, designed to probe complementary ranges of space, time, and energy.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Mechanistic insights into N 2 O formation as a side product in NH 3 -SCR over small pore Cu-zeolites

Here, the present contribution provides clarity to N 2 O formation mechanisms and key influencing factors during low temperature NH 3 -SCR, with the goal of enabling the rational design of advanced SCR catalysts with low greenhouse gas impact. By studying more than 50 small pore Cu-exchanged zeolite SCR catalyst samples, including model catalysts synthesized in our laboratories and state-of-the-art industrial catalysts, we explored a wide range of factors affecting N 2 O formation. These factors included Cu loading, support Si/Al ratio, support topology, catalyst aging, reaction temperature and reactant feed composition effects. We probed N 2 O formation under both steady-state SCR, and during NH 4 NO 3 decomposition via temperature programmed desorption (TPD). Finally, we used DFT to probe energetics of possible N 2 O formation pathways. Based on these studies, we confirm that low temperature N 2 O formation occurs via multiple reaction pathways that all involve NH 4 NO 3 and are supported by Cu moieties that facilitate in-situ NO oxidation to NO 2 .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Steam reforming of fast pyrolysis-derived aqueous phase oxygenates over Co, Ni, and Rh metals supported on MgAl 2 O 4

In this study we examine feasibility for steam reforming the mixed oxygenate aqueous fraction derived from mildly hydrotreated fast pyrolysis bio-oils. Catalysts selective towards hydrogen formation and resistant to carbon formation utilizing feeds with relatively low steam-to-carbon (S/C) ratios are desired. Rh (5 wt%), Pt (5 wt%), Ru (5 wt%), Ir (5 wt%), Ni (15 wt%), and Co (15 wt%) metals supported on MgAl 2 O 4 were evaluated for catalytic performance at 500°C and 1 atm using a complex feed mixture comprising of acids, polyols, cycloalkanes, and phenolic compounds. The Rh catalyst was found to be the most active and resistant to carbon formation. The Ni and Co catalysts were found to be more active than the other noble metal catalysts investigated (Pt, Ru, and Ir). However, Ni was found to form significantly more carbon (coke) on the catalyst surface. Furthermore, Co was found to be the most selective towards H 2 formation. Evaluating the effect of temperature on stability for the Rh catalyst we found that catalyst stability was best when operated at 500°C as compared to the higher temperatures investigated (700, 800°C). When operating at 700°C significantly more graphitic formation was observed on the spent catalyst surface. Operating at 800°C resulted in reactor plugging as a result of thermal decomposition of the reactants. Thus, a concept analogous to the petroleum industries’ use of a pre-reformer, operated at approximately 500°C for steam reforming of the heavier naphtha components, followed by a high temperature methane reforming operated in the 600-850°C temperature range, could be applied in the case of steam reforming biomass derived oxygenates. Moreover, stability evaluations were performed over the Rh, Ni, and Co catalysts at 500°C and 1 atm, under similar initial conversions, reveal the Co catalyst to be the most stable and selective towards H 2 production. Conversion and selectivity to CH 4 over Co remained relatively stable at approximately 80% and 1.2%, respectively. By contrast, the Rh and Ni catalysts CH 4 selectivity’s were approximately 7-8%. Thus suggesting that a Co type catalyst may be more suitable for the steam reforming of biomass derived oxygenates as compared to the more conventional Ni and Rh type steam reforming catalysts. However, deposition of carbon on the surface was observed. High resolution TEM on the spent catalysts revealed the formation of graphitic carbon on the Rh catalyst, and filamentous carbon formation was observed on both the Ni and Co catalysts, albeit less pronounced on Co. Thus there is certainly opportunity for improvement in Co catalyst design and/or with process optimization.

aqueous phase↗
DOE OSTI2026

Methyl formate oxidation kinetics up to 100 atm

Methyl formate (MF, CH3OCHO), the simplest ester, is a representative oxygenated fuel with high oxygen content, and low sooting tendency. However, its oxidation behavior under high-pressure and intermediate-temperature conditions remains insufficiently understood, especially where low-temperature peroxy radical chemistry, methanol chemistry, and pressure-dependent reaction pathways play a critical role. In this study, MF oxidation experiments were conducted in the Princeton supercritical-pressure jet-stirred reactor (SP-JSR) at 20 and 100 atm over the temperature range of 400–950 K under both fuel-lean and fuel-rich conditions. Based on the experimental results, an updated HP-Mech was developed by incorporating previous MF sub-mechanisms, expanded low-temperature peroxy pathways, and evaluated pressure-dependent decomposition kinetics. The newly updated HP-Mech shows greatly improved performance in predicting the onset temperature, the key intermediate species fractions, methanol formation, and the progression of MF oxidation across all the experimental conditions. Path flux analysis indicates that MF consumption at the onset stage is dominated by H-abstraction at the methyl site, forming CH2OCHO radicals that lead to the formation and isomerization of O2CH2OCHO, driving low-temperature chain propagation. Moreover, H-abstraction at the formate site forms CH3OCO radicals that preferentially decompose to CH3, initiating the methanol formation pathway linked to CH3O2 and HO2 chemistry. At the same time, HO2 formation is strongly coupled to MF oxidation through multiple MF-derived radical pathways. HCO originates from MF oxidation and acts as a key coupling species linking fuel consumption to HO2 buildup, especially under high-pressure and intermediate-temperature conditions. In addition to this dominant channel, supplementary HO2 formation pathways involving CH3, CH3O, CH2OH, and CH3O2 reacting with O2 further connect methanol chemistry and oxygenated radical chemistry to the HO2 pool, indicating the central role of HO2 in governing MF oxidation. Sensitivity analysis identifies MF with OH/HO2/CH3O2 reactions and the HO2/H2O2/OH sequence as the key factors controlling reactivity in the high-pressure and intermediate-temperature regime. MF directly reacts with OH/HO2/CH3O2 to consume the fuel and produce reactive radicals like CH2OCHO and CH3OCO that undergo subsequent oxidation pathways. Moreover, HO2 recombination suppresses oxidation at lower temperatures, while thermal decomposition of H2O2 accelerates OH production and promotes fuel consumption as temperature increases. The direct formation of active OH from HO2 radicals further completes the mechanism, improving its prediction especially during the oxidation onset stage.

Low-temperature Chemistry↗
DOE OSTI2017

Synthesis and VOC degradation ability of a CeO{sub 2}/WO{sub 3} thin-layer visible-light photocatalyst

Highlights: • Plasma-synthesized γ/ε-WO{sub 3} showed improvement of acetaldehyde decomposition. • Ferroelectricity of ε-WO{sub 3} slowed hole-electron recombination. • Synergistic effect between WO{sub 3} and CeO{sub 2} further enhanced photocatalytic activity. - Abstract: The plasma synthesis, characterization, and photocatalytic activity of WO{sub 3}, which consisted of a mixture of gamma WO{sub 3} and epsilon WO{sub 3} (γ/ε-WO{sub 3}), and physically mixed WO{sub 3} and CeO{sub 2} (WO{sub 3}/CeO{sub 2}) were investigated. Synergistic effects were observed in acetaldehyde photocatalysis experiments using γ/ε-WO{sub 3} or WO{sub 3}/CeO{sub 2}. The synergistic effect in the γ/ε-WO{sub 3} photocatalyst system is proposed to be the concurrent reduction of oxygen at gamma WO{sub 3} and oxidation of acetaldehyde at epsilon WO{sub 3}. It is hypothesized that acetaldehyde preferentially interacts with epsilon WO{sub 3} over gamma WO{sub 3} because of dipole–dipole interactions between them. In the case of the WO{sub 3}/CeO{sub 2} photocatalyst, the electron scavenging property of CeO{sub 2} aided charge carrier separation. As a result, WO{sub 3}/CeO{sub 2} exhibited excellent photocatalytic activity in volatile organic compound decomposition under visible light at room temperature.

36 MATERIALS SCIENCE↗
DOE OSTI2021

High resolution measurements reveal abiotic and biotic mechanisms of elevated nitric oxide emission after wetting dry soil

Wetting dry soil triggers emission of nitric oxide (NO), which can harm air quality and influence ecosystem N balance. NO released after wetting may be derived from two primary mechanisms: (1) abiotic decomposition of nitrite (NO 2 -) present in the dry soil and (2) biologically-mediated production of NO. The relative contributions of these mechanisms to NO emission are challenging to partition. To differentiate the two mechanisms, we made continuous observations of NO emission from a range of soils that varied in texture, pH, and exchangeable cations. Additionally, we coupled NO gas exchange measurements with automated, non-destructive high-resolution sampling of inorganic N species via microdialysis. We identified two distinct phases of NO production (1) an initial phase that reached its maximum less than 30 min after rewetting; and (2) a second phase lasting up to 36 h. The magnitude of the initial phase of NO production was correlated with the initial nitrous acid concentration (calculated from NO 2 - concentrations and soil pH) and soil exchangeable calcium. The second phase of NO emission coincided with a peak in NO 2 - that preceded NO 3 - accumulation. Together, these results suggest that NO emissions following wetting are defined by an initial pulse of abiotic NO formation mediated by soil acidity at mineral surfaces, followed by a prolonged pulse of NO emission driven by a lag between the biological processes of ammonia oxidation and nitrite oxidation. These results can inform mechanistic models of NO emissions from soils to improve predictions of the terrestrial N cycle and atmospheric chemistry.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2018

Solubility and Complexation of the Bismuthate Ion in Nitric Acid Systems

Here, the dissolution rate and solubility of NaBiO 3 have been investigated in nitric acid systems ranging from 4–6 M HNO 3 , and were found to be 58–76 µg/cm 2 ·d and 490–830 mM, respectively. The presence of 50 mM U(VI) drastically increased the solubility to 540–1200 mM, while rates of dissolu-tion were relatively unchanged. The solubility of NaBiO 3 increased with an increase in U(VI) con-centrations at 4 M HNO 3 , with log-log analysis indicating a one-to-one complex between Bi and U and IR spectroscopic evidence monitoring uranyl stretching suggesting complex formation. Absorb-ance spectra were obtained experimentally and computationally with an absorbance band in the range of 450–600 nm that has been attributed to Bi(V). The ingrowth and decay of Bi(V) in solution was also studied as a function of mass of solid NaBiO 3 present, acidity, and temperature. The ac-tivation energies of dissolution and decomposition were calculated to be 39 ± 4 and 61 ± 6 kJ/mol, re-spectively. Furthermore, these results indicate that dissolution of NaBiO 3 into the respective Na + and BiO 3 – is occur-ring prior to undergoing reduction, a process which conventionally has been believed to occur in the reverse order.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2015

The Role of Cesium Cation in Controlling Interphasial Chemistry on Graphite Anode in Propylene Carbonate-Rich Electrolytes

Propylene carbonate (PC) is seldom used in lithium-ion batteries (LIBs) due to its sustained co-intercalation into graphene structure and the eventual graphite exfoliation, despite potential advantages it brings, such as wider liquid range and lower cost. Here we discover that cesium cation (Cs+), originally used to suppress dendrite growth of Li metal anode, directs the formation of solid electrolyte interphase (SEI) on graphitic anode in PC-rich electrolytes through preferential solvation. Effective suppression of PC-decomposition and graphite-exfoliation was achieved when the ratio of ethylene carbonate (EC)/PC in electrolytes was so adjusted that the reductive decomposition of Cs+-(EC)m (1≤m≤2) complex precedes that of Li+-(PC)n (3≤n≤5). The interphase directed by Cs+ is stable, ultrathin and compact, leading to significant improvements in LIB performances. In a broader context, the accurate tailoring of SEI chemical composition by introducing a new solvation center represents a fundamental breakthrough in manipulating interfacial reactions processes that once were elusive.

cesium cation↗
DOE OSTI2022

Mineral Protection and Resource Limitations Combine to Explain Profile-Scale Soil Carbon Persistence

The fate of soil carbon (C) is largely controlled by microbial oxidation of organic matter (OM), which is constrained by a variety of mechanisms. OM association with soil minerals provides pronounced protection against microbial decomposition. However, factors such as climate, occlusion, and resource limitations also contribute to OM preservation. Here, we explore the factors explaining C distribution and age within an upland rainforest soil in Hawai'i, a site with abundant preferential flow paths (PFPs) and high short-range order (SRO) mineral content. We characterized lateral and vertical changes in Δ 14 C, SRO mineral content, C-functional group chemistry, and microbial community composition to elucidate the contributions of multiple protection mechanisms to OM preservation. Consistent with our expectation, SRO mineral content and Δ 14 C were strongly correlated (R 2 = 0.95), indicating strong mineral protection of OM throughout the profile. Surprisingly, distance from PFP was also a significant predictor of Δ 14 C and improved model fit, particularly in the shallow horizons (R 2 = 0.97). Elevated C/N ratios, decreased microbial abundance, and greater SRO mineral content suggest nitrogen limitations and enhanced mineral protection constrain OM turnover with distance from PFPs in deep, subsurface mineral horizons. Steady microbial abundance, increasing putative anaerobe abundance, and changes in C-functional group chemistry indicate oxygen limitations constrain OM turnover in the matrix of shallow mineral horizons. Given that oxygen and nutrient limitations contribute to OM preservation in this high SRO system—an exemplar of mineral protection—resource limitations may play an even more important role in OM preservation in other well-structured soils.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2019

Electrical conductivity, ion pairing, and ion self-diffusion in aqueous NaCl solutions at elevated temperatures and pressures

We have performed classical molecular dynamics (MD) simulations of aqueous sodium chloride (NaCl) solutions from 298 to 674 K at 200 bars to understand the influence of ion pairing and ion self-diffusion on electrical conductivity in high-temperature/high-pressure salt solutions. Conductivity data obtained from the MD simulation highlight an apparent anomaly, namely, a conductivity maximum as temperature increases along an isobar, which has been also observed in experimental studies. By examining both velocity autocorrelation and cross-correlation terms of the Green-Kubo integral, we quantitatively demonstrate that the conductivity anomaly arises mainly from a competition between the single-ion self-diffusion and the contact ion pair formation. The velocity autocorrelation function in conjunction with structural analysis suggests that diffusive motion of ions is suppressed at high temperatures due to the persistence of an inner hydration shell. Here, the contribution of velocity cross-correlation functions between oppositely charged ions becomes significant at the onset of the conductivity decrease. Structural analysis based on Voronoi tessellation and pair correlation functions indicates that the fraction of contact ion pairs increases as temperature increases. Spatial decomposition of the electrical conductivity also indicates that the formation of contact ion pairs significantly decreases the electrical conductivity compared to Nernst-Einstein conductivity, but the contribution of distant opposite charges cannot be ignored except at the highest temperature due to unscreened long-range interactions.

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

Quantified Gamow shell model interaction for p s d -shell nuclei

Background: The structure of weakly bound and unbound nuclei close to particle drip lines is one of the major science drivers of nuclear physics. A comprehensive understanding of these systems goes beyond the traditional configuration interaction approach formulated in the Hilbert space of localized states (nuclear shell model) and requires an open quantum system description. The complex-energy Gamow shell model (GSM) provides such a framework as it is capable of describing resonant and nonresonant many-body states on equal footing. Purpose: To make reliable predictions, quality input is needed that allows for the full uncertainty quantification of theoretical results. In this study, we carry out the optimization of an effective GSM (one-body and two-body) interaction in the psdf-shell-model space. The resulting interaction is expected to describe nuclei with 5 ≤ A ≲ 12 at the p-sd-shell interface. Method: The one-body potential of the 4 He core is modeled by a Woods-Saxon + spin-orbit + Coulomb potential, and the finite-range nucleon-nucleon interaction between the valence nucleons consists of central, spin-orbit, tensor, and Coulomb terms. The GSM is used to compute key fit observables. The χ 2 optimization is performed using the Gauss-Newton algorithm augmented by the singular value decomposition technique. The resulting covariance matrix enables quantification of statistical errors within the linear regression approach. Results: The optimized one-body potential reproduces nucleon- 4 He scattering phase shifts up to an excitation energy of 20 MeV. The two-body interaction built on top of the optimized one-body field is adjusted to the bound and unbound ground-state binding energies and selected excited states of the helium, lithium, and beryllium isotopes up to A = 9 . A very good agreement with experimental results was obtained for binding energies. First applications of the optimized interaction include predictions for two-nucleon correlation densities and excitation spectra of light nuclei with quantified uncertainties. In conclusion: The new interaction will enable comprehensive and fully quantified studies of structure and reactions aspects of nuclei from the psd region of the nuclear chart.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗