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DOE OSTI2016

BROAD [C II] LINE WINGS AS TRACER OF MOLECULAR AND MULTI-PHASE OUTFLOWS IN INFRARED BRIGHT GALAXIES

We report a tentative correlation between the outflow characteristics derived from OH absorption at 119 μ m and [C ii] emission at 158 μ m in a sample of 22 local and bright ultraluminous infrared galaxies (ULIRGs). For this sample, we investigate whether [C ii] broad wings are a good tracer of molecular outflows, and how the two tracers are connected. Fourteen objects in our sample have a broad wing component as traced by [C ii], and all of these also show OH119 absorption indicative of an outflow (in one case an inflow). The other eight cases, where no broad [C ii] component was found, are predominantly objects with no OH outflow or a low-velocity (≤100 km s{sup −1}) OH outflow. The FWHM of the broad [C ii] component shows a trend with the OH119 blueshifted velocity, although with significant scatter. Moreover, and despite large uncertainties, the outflow masses derived from OH and broad [C ii] show a 1:1 relation. The main conclusion is therefore that broad [C ii] wings can be used to trace molecular outflows. This may be particularly relevant at high redshift, where the usual tracers of molecular gas (like low-J CO lines) become hard to observe. Additionally, observations of blueshifted Na i D λλ 5890, 5896 absorption are available for 10 of our sources. Outflow velocities of Na i D show a trend with OH velocity and broad [C ii] FWHM. These observations suggest that the atomic and molecular gas phases of the outflow are connected.

79 ASTRONOMY AND ASTROPHYSICS↗

DOE OSTI2018

Fusion hindrance for the positive Q -value system C 12 + Si 30

Here, the fusion reaction 12 C+ 30 Si is a link between heavier cases studied in recent years, and the light heavy-ion systems, e.g., 12 C+ 12 C, 16 O+ 16 O that have a prominent role in the dynamics of stellar evolution. 12 C+ 30 Si fusion itself is not a relevant process for astrophysics, but it is important to establish its behavior below the barrier, where couplings to low-lying collective modes and the hindrance phenomenon may determine the cross sections. The excitation function is presently completely unknown below the barrier for the 12 C+ 30 Si reaction, thus no reliable extrapolation into the astrophysical regime for the C+C and O+O cases can be performed.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

DOE OSTI2013

Measurement of the C P violation parameters in B 0 → π + π - decays

We present a measurement of the charge-parity ( C P ) violating parameters in B 0 → π + π - decays. The results are obtained from the final data sample containing 772 × 10 6 B B ¯ pairs collected at the Υ ( 4 S ) resonance with the Belle detector at the KEKB asymmetric-energy e + e - collider. We obtain the C P violation parameters A C P ( B 0 → π + π - ) = + 0.33 ± 0.06 ( stat ) ± 0.03 ( syst ) , S C P ( B 0 → π + π - ) = - 0.64 ± 0.08 ( stat ) ± 0.03 ( syst ) , where A C P and S C P represent the direct and mixing-induced C P asymmetries in B 0 → π + π - decays, respectively. Using an isospin analysis including results from other Belle measurements, we find 23.8 ° < Φ 2 < 66.8 ° is disfavored at the 1 σ level, where Φ 2 is one of the three interior angles of the Cabibbo-Kobayashi-Maskawa unitarity triangle related to B u , d decays.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

DOE OSTI2024

The multifaceted role of c-di-AMP signaling in the regulation of Porphyromonas gingivalis lipopolysaccharide structure and function

This study unveils the intricate functional association between cyclic di-3’,5’-adenylic acid (c-di-AMP) signaling, cellular bioenergetics, and the regulation of lipopolysaccharide (LPS) profile in Porphyromonas gingivalis, a Gram-negative obligate anaerobe considered as a keystone pathogen involved in the pathogenesis of chronic periodontitis. Previous research has identified variations in P. gingivalis LPS profile as a major virulence factor, yet the underlying mechanism of its modulation has remained elusive. We employed a comprehensive methodological approach, combining two mutants exhibiting varying levels of c-di-AMP compared to the wild type, alongside an optimized analytical methodology that combines conventional mass spectrometry techniques with a novel approach known as FLAT n . We demonstrate that c-di-AMP acts as a metabolic nexus, connecting bioenergetic status to nuanced shifts in fatty acid and glycosyl profiles within P. gingivalis LPS. Notably, the predicted regulator gene cdaR, serving as a potent regulator of c-di-AMP synthesis, was found essential for producing N-acetylgalactosamine and an unidentified glycolipid class associated with the LPS profile. The multifaceted roles of c-di-AMP in bacterial physiology are underscored, emphasizing its significance in orchestrating adaptive responses to stimuli. Furthermore, our findings illuminate the significance of LPS variations and c-di-AMP signaling in determining the biological activities and immunostimulatory potential of P. gingivalis LPS, promoting a pathoadaptive strategy. The study expands the understanding of c-di-AMP pathways in Gram-negative species, laying a foundation for future investigations into the mechanisms governing variations in LPS structure at the molecular level and their implications for host-pathogen interactions.

59 BASIC BIOLOGICAL SCIENCES↗

DOE OSTI2022

Stable binding to phosphatidylserine-containing membranes requires conserved arginine residues in tandem C domains of blood coagulation factor VIII

At sites of vascular damage, factor VIII (fVIII) is proteolytically activated by thrombin and binds to activated platelet surfaces with activated factor IX (fIXa) to form the intrinsic “tenase” complex. Previous structural and mutational studies of fVIII have identified the C1 and C2 domains in binding to negatively charged membrane surfaces through β-hairpin loops with solvent-exposed hydrophobic residues and a ring of positively charged basic residues. Several hemophilia A-associated mutations within the C domains are suggested to disrupt lipid binding, preventing formation of the intrinsic tenase complex. In this study, we devised a novel platform for generating recombinant C1, C2, and C1C2 domain constructs and performed mutagenesis of several charged residues proximal to the putative membrane binding region of each C domain. Binding measurements between phosphatidylserine (PS)-containing lipid membrane surfaces and fVIII C domains demonstrated an ionic strength dependence on membrane binding affinity. Mutations to basic residues adjacent to the surface-exposed hydrophobic regions of C1 and C2 differentially disrupted membrane binding, with abrogation of binding occurring for mutations to conserved arginine residues in the C1 (R2163) and C2 (R2320) domains. Lastly, we determined the X-ray crystal structure of the porcine fVIII C2 domain bound to o-phospho-L-serine, the polar headgroup of PS, which binds to a basic cleft and makes charge-charge contact with R2320. We conclude that basic clefts in the fVIII C domains bind to PS-containing membranes through conserved arginine residues via a C domain modularity, where each C domain possesses modest electrostatic-dependent affinity and tandem C domains are required for high affinity binding.

59 BASIC BIOLOGICAL SCIENCES↗

NASA NTRS2003

The [C II] 158 Micron Line in Ultraluminous Infrared Galaxies Revisited

We present a study of the [C II] 157.74 micron fine-structure line in a sample of 15 ultraluminous infrared (IR) galaxies (IR luminosity L(sub IR greater than or equal to 10(exp 12)L.; ULIRGs) using the Long Wavelength Spectrometer (LWS) on the Infrared Space Observatory (ISO). We confirm the observed order of magnitude deficit (compared to normal and starburst galaxies) in the strength of the [C II] line relative to the far-infrared (FIR) dust continuum emission found in our initial report, but here with a sample that is twice as large. This result suggests that the deficit is a general phenomenon affecting 4 out of 5 ULIRGs. We present an analysis using observations of generally acknowledged photodissociation region (PDR) tracers ([C II], [OI] 63 and 145 micron, and FIR continuum emission), which suggests that a high ultraviolet flux G(sub 0) incident on a moderate density n PDR could explain the deficit. However, comparisons with other ULIRG observations, including CO (1-0), [C I] (1-0), and 6.2 micron polycyclic aromatic hydrocarbon (PAH) emission, suggest that high G(sub 0)/n PDRs alone cannot produce a self-consistent solution that is compatible with all of the observations. We propose that non-PDR contributions to the FIR continuum can explain the apparent [C II] deficiency. Here, unusually high G(sub 0) and/ or n physical conditions in ULIRGs as compared to those in normal and starburst galaxies are not required to explain the [C II] deficit. Dust-bounded photoionization regions, which generate much of the FIR emission but do not contribute significant [C II] emission, offer one possible physical origin for this additional non-PDR component. Such environments may also contribute to the observed suppression of FIR fine-structure emission from ionized gas and PAHs, as well as the warmer FIR colors found in ULIRGs. The implications for observations at higher redshifts are also revisited.

Luhman, M. L.↗

DOE OSTI2014

Evidence of Υ ( 1 S ) → J / ψ + χ c 1 and search for double-charmonium production in Υ ( 1 S ) and Υ ( 2 S ) decays

Using data samples of 102 × 10 6 Υ ( 1 S ) and 158 × 10 6 Υ ( 2 S ) events collected with the Belle detector, a first experimental search has been made for double-charmonium production in the exclusive decays Υ ( 1 S , 2 S ) → J / ψ ( ψ ' ) + X , where X = η c , χ c J ( J = 0 , 1 , 2 ) , η c ( 2 S ) , X ( 3940 ) , and X ( 4160 ) . No significant signal is observed in the spectra of the mass recoiling against the reconstructed J / ψ or ψ ' except for the evidence of χ c 1 production with a significance of 4.6 σ for Υ ( 1 S ) → J / ψ + χ c 1 . The measured branching fraction B ( Υ ( 1 S ) → J / ψ + χ c 1 ) is [ 3.90 ± 1.21 ( stat ) ± 0.23 ( syst ) ] × 10 - 6 . The 90% C.L. upper limits on the branching fractions of the other modes having a significance of less than 3 σ are determined. In conclusion, these results are consistent with theoretical calculations using the nonrelativistic QCD factorization approach.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

DOE OSTI2013

Observation of the Decay B c + → B s 0 π +

The result of a search for the decay B c + → B s 0 π + is presented, using the B s 0 → D s - π + and B s 0 → J /ψφ channels. The analysis is based on a data sample of pp collisions collected with the LHCb detector, corresponding to an integrated luminosity of 1 fb -1 taken at a center-of-mass energy of 7 TeV, and 2 fb -1 taken at 8 TeV. The decay B c + → B s 0 π + is observed with significance in excess of 5 standard deviations independently in both decay channels. The measured product of the ratio of cross sections and branching fraction is [σ (B c + )/σ (B s 0 )] × B ( B c + → B s 0 π + ) =[2.37±0.31 (stat) ± 0.11 (syst)$ +0.17\atop{-0.13} $(τ$_B{_c^+}$)]×10 -3 , in the pseudorapidity range 2<η(B)<5, where the first uncertainty is statistical, the second is systematic, and the third is due to the uncertainty on the $B{_c^+}$ lifetime. This is the first observation of a B meson decaying to another B meson via the weak interaction.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

DOE OSTI2020

X-ray photoelectron spectroscopy and rotating disk electrode measurements of smooth sputtered Fe-N-C films

Electrocatalysts for the oxygen reduction reaction (ORR) based on complexes of iron and nitrogen in a carbon matrix (Fe-N-C) are a promising alternative to platinum group metal (PGM) based catalysts in polymer electrolyte membrane (PEM) fuel cells. Further improvements of Fe-N-C catalysts would benefit from model thin film studies of activity and stability of catalytic sites, but synthesis of Fe-N-C model thin films is challenging. Here we report on synthesis and characterization of Fe-N-C thin films produced by co-sputtering iron and carbon in a reactive nitrogen atmosphere onto removable glassy carbon rotating disk electrode (RDE) tips. Scanning electron microscopy (SEM) measurements indicate that the Fe-N-C films deposited at high temperature are smoother than the films annealed at high temperature. Electrocatalytic activity measured on the thin Fe-N-C films is greater for both high-temperature samples than for the room-temperature sample. From the analysis of X-ray photoelectron spectroscopy (XPS) data, exposure of the films to high temperatures results in increased graphitization of the carbon with the Fe-N-C films, and increased relative amount of graphitic and hydrogenated nitrogen species. Overall the results of this study demonstrate the feasibility of a thin film model system approach for studying active sites in PGM-free catalysts.

14 SOLAR ENERGY↗

DOE OSTI2020

Selective activation of methane C–H bond in the presence of methanol

Direct methane to methanol (MTM) conversion over heterogeneous catalysts is a promising route for valorization of methane. The methane C-H bond activation is considered as the key step of the MTM and is the focus of considerable research activity. However, the formed methanol typically suffers from overoxidation largely due to the cleavage of a methanol C-H bond, whose bond dissociation energy is ca. 0.5 eV lower than that of the methane C-H bond, which usually translates to a transition state energy of the methanol C-H bond cleavage that is ca. 0.55 eV lower than that of methane whenever the reactions proceed through a radical mechanism. Furthermore, we propose a general approach for decreasing the transition state energy difference between the CH 4 and CH 3 OH C-H bond dissociation. When a metal-oxide supported cationic transition metal atom and a neighboring oxygen on the oxide surface serve as the active site, the transition state energy difference through a surface-stabilized pathway can be noticeably narrowed as compared with that of a radical pathway. For Ir, Pt and Rh-doped anatase TiO 2 (101), the CH 4 C-H bond activation can be preferred over that of CH 3 OH at significant methanol mole fraction. Also, for PdAu alloys containing adsorbed oxygen and positively charged Pd, calculations suggest in agreement with recent experiments (Science 367 (6474), 193-197) that the CH 4 C-H bond can be selectively activated in the presence of CH 3 OH.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2025

Benchmarking fast-neutron response of 7 Li-enriched C 7 LYC scintillators: Simulations and experiment

New insights into the fast neutron response of 7 Li-enriched C 7 LYC scintillators have been obtained through detailed Geant4 simulations of 35 Cl(n,p) and 35 Cl(n, α) reactions that are primarily responsible for the fast neutron response of C 7 LYC. The light output of a 1” x1” C 7 LYC detector was simulated using the Birks equation for light quenching in scintillators. The simulations were benchmarked against neutron scattering data from a 12 C target obtained with a white neutron beam at the Los Alamos LANSCE facility and fourteen 1”x1” C 7 LYC detectors. Incident neutron energies extracted from time-of-flight measurements, and appropriate recoil corrections for the different detector angles were used to map the response of C 7 LYC to mono-energetic neutrons. Resonances in the 35 Cl(n,p) reaction cross-section below 3 MeV incident neutron energy were directly observed in C 7 LYC. The experimental data and simulations are compared with ENDF databases, as well as recent direct cross-section measurements of neutrons scattered from a 35 Cl target. In conclusion, the results suggest a scrutiny of the 35 Cl(n,p) and 35 Cl(n, α) cross sections at low energy in the ENDF library.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

DOE OSTI2025

Higher levels of mixed-linkage (1,3;1,4)-β-glucan in transgenic grasses may impact soil C processing

Carbohydrates, including mixed-linkage glucan (MLG), in grass cell walls make them a valuable potential feedstock for biofuel production. Hence, the development of transgenic grasses with elevated levels of MLG is being actively pursued worldwide. Changes in chemical and physical root characteristics of MLG-overproducing transgenic plants can affect processing of the root-derived carbon (C) by soil microorganisms, impacting soil C cycling. Here, this study is the first attempt to elucidate the impact of MLG-related genetic modifications on root traits, root decomposition, and soil C processing. We explored four genotypes of Brachypodium ( Brachypodium distachyon ): a wildtype, a loss-of-function mutant with low MLG, an MLG overexpressing line, and a line lacking MLG hydrolase (with high MLG), incubating their roots in soils of two contrasting vegetation histories: monoculture switchgrass and polyculture restored prairie. The four genotypes exhibited contrasting root MLG and soluble sugar concentrations, and different growth phenotypes. Roots with the highest MLG content resulted in a ∼55 % increase in microbial biomass C compared to wildtype in both soils. However, the genotype effects on C mineralization rates were influenced by the vegetation history, with significant effects observed only in the soil from switchgrass but not prairie origin. While further work is required to understand the full impact of MLG-overproducing plants on soil C accrual, our findings suggest that their influence on soil C processes cannot be discounted.

Brachypodium distachyon↗

DOE OSTI2017

Field Degassing as a New Sampling Method for 14 C Analyses in Old Groundwater

Radiocarbon ( 14 C) activity in groundwater can be used to determine subsurface residence time up to ~40 kyr, providing crucial information on dynamic properties of groundwater and on paleoclimate. However, commonly applied sampling methods for dissolved inorganic carbon (DIC- 14 C) are prone to low level of modern atmospheric contamination, resulting in underestimation of groundwater ages that cluster around 30–40 kyr. We extract CO 2 gas from groundwater using a device originally developed for studies of noble gas radionuclides. Carbon is collected in the gas phase, eliminating the possibility of fostering microbial activities and aqueous chemical reactions during sample storage. This method collects CO 2 - 14 C and radiokrypton ( 81 Kr and 85 Kr) samples simultaneously. The presence of any shorter-lived 85 Kr is used to evaluate the degree of atmospheric contamination during sampling or mixing of young groundwater. Most groundwater samples showed lower CO 2 - 14 C activities than those of DIC- 14 C, presumably due to the absence of atmospheric contamination. Samples with 81 Kr age exceeding 150 kyr have no detectable CO 2 - 14 C except where mixing sources of young groundwater is suspected. Furthermore these field data serve as confirmations for the reliability of the newly presented sample collection and CO 2 - 14 C method, and for the outstanding roles of radiokrypton isotopes in characterizing old groundwater.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2025

Constraining the Low-Temperature Oxidation Mechanism of n -Hexanol through the Detection and Identification of C 6 Elusive Intermediates

Alcohol-based fuels are currently considered to be viable energy carriers for the transportation sector. Consequently, a comprehensive mechanistic understanding of the low-temperature oxidation of alcohols is essential for application in advanced low-temperature compression engines. Here, in this work, a multidimensional approach involving experimental investigations, kinetic modeling, and theoretical calculations was used to provide new insights into the low-temperature oxidation mechanism of a C 6 alcohol, n -hexanol (CH 3 (CH 2 ) 5 OH), through the detection and identification of elusive C 6 intermediates. The oxidation of n-hexanol was investigated in a jet-stirred reactor under stoichiometric conditions (ϕ = 1.0), an initial fuel concentration of 2%, a residence time of 2 s, a temperature range between 500 and 660 K, and a pressure of 700 Torr. The reactants, intermediates, and final products were detected and identified by means of molecular-beam mass spectrometry coupled with single-photon ionization employing tunable synchrotron-generated vacuum ultraviolet radiation. Chemical kinetic simulations were performed using a previously published kinetic model (Togbé et al., Energy Fuels 2010, 11, 5859−5875) to predict the reactivity of n-hexanol and elucidate the predominant formation pathways of the observed low-temperature species. Experimental photoionization efficiency curves in conjunction with ab initio calculations, enabled the identification of important low-temperature species, such as C 6 unsaturated alcohols, C 6 olefinic hydroperoxides, C 6 cyclic ethers, C 6 diones, and C 6 ketohydroperoxides. The results of this study provide valuable insight into the mechanism of the low-temperature oxidation chemistry of n -hexanol, contributing to the development of kinetic models for the low-temperature oxidation of n-hexanol and other long-chain linear alcohols.

alcohols↗

DOE OSTI2020

Rational Design and Synthesis of Hierarchical Porous Mn–N–C Nanoparticles with Atomically Dispersed MnNx Moieties for Highly Efficient Oxygen Reduction Reaction

Developing transition-metal excluding iron and cobalt–nitrogen–carbon (M–N–C) electrocatalysts for the oxygen reduction reaction (ORR) is critical to substantially promote the development of precious-metal-free metal–air batteries and fuel cells. In the work, Mn–N–C nanoparticles with atomically dispersed MnNx moieties were synthesized by pyrolyzing Mn-ion–dual-pyridine coordinated complex, which was obtained via a simple condensation reaction between 2,6-diamino-pyridine and 2,6-diacetyl-pyridine with MnCl 2 as the Mn source. The precursor features with a characteristic structure of dual-pyridine ligand, which possesses a strong coordinating capability for Mn 2+ , facilitating the formation of highly dispersed nitrogen-coordinated Mn sites (MnN x ). Attributed to the highly active atomic MnN x sites, hierarchical pore structure, and high surface area of the Mn–N–C derived from the new precursor, it exhibits outstanding ORR performance in 0.1 M KOH with an almost direct four-electron reaction path and high selectivity of O 2 into H 2 O (low H2O2 production <3.5%). The half-wave potential of Mn–N–C is 0.88 V vs RHE, which is 20 mV higher than that of commercial Pt/C catalyst and reaches to the level of Fe–N–C catalyst obtained by the same method. Meanwhile, the feasibility of Mn–N–C for practical application is validated by its higher-performance power output in Zn–air battery with a maximum power density of 132 mW cm –2 compared to that of Pt/C (121 mW cm –2 ) using the same catalyst loading of 1.0 mg cm –2 . This work develops a convenient route to develop non-Fe or Co–N–C electrocatalyst for the ORR.

36 MATERIALS SCIENCE↗

DOE OSTI2022

13 C ENDOR Characterization of the Central Carbon within the Nitrogenase Catalytic Cofactor Indicates That the CFe 6 Core Is a Stabilizing “Heart of Steel”

Substrates and inhibitors of Mo-dependent nitrogenase bind and react at Fe ions of the active-site FeMo-cofactor [7Fe–9S–C–Mo–homocitrate] contained within the MoFe protein α-subunit. The cofactor contains a CFe 6 core, a carbon centered within a trigonal prism of six Fe, whose role in catalysis is unknown. Targeted 13 C labeling of the carbon enables electron-nuclear double resonance (ENDOR) spectroscopy to sensitively monitor the electronic properties of the Fe–C bonds and the spin-coupling scheme adopted by the FeMo-cofactor metal ions. Here this report compares 13 CFe 6 ENDOR measurements for (i) the wild-type protein resting state (E 0 ; α-Val 70 ) to those of (ii) α-Ile 70 , (iii) α-Ala 70 -substituted proteins; (iv) crystallographically characterized CO-inhibited “hi-CO” state; (v) E 4 (4H) Janus intermediate, activated for N 2 binding/reduction by accumulation of 4[ e– /H + ]; (vi) E 4 (2H)* state containing a doubly reduced FeMo-cofactor without Fe-bound substrates; and (vii) propargyl alcohol reduction intermediate having allyl alcohol bound as a ferracycle to FeMo-cofactor Fe6. All states examined, both S = 1/2 and 3/2 exhibited near-zero 13 C isotropic hyperfine coupling constants, $^Ca$ = [-1.3 ↔ +2.7] MHz. Density functional theory computations and natural bond orbital analysis of the Fe-C bonds show that this occurs because a (3 spin-up/3 spin-down) spin-exchange configuration of CFe 6 Fe-ion spins produces cancellation of large spin-transfers to carbon in each Fe–C bond. Previous X-ray diffraction and DFT both indicate that trigonal-prismatic geometry around carbon is maintained with high precision in all these states. The persistent structure and Fe–C bonding of the CFe 6 core indicate that it does not provide a functionally dynamic (hemilabile) “beating heart”-instead it acts as “a heart of steel”, stabilizing the structure of the FeMo-cofactor-active site during nitrogenase catalysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2024

Mechanistic Insights into the Origins of Selectivity in a Cu-Catalyzed C–H Amidation Reaction

The catalytic transformation of C-H to C-N bonds offers rapid access to fine chemicals and high-performance materials, but achieving high selectivity from undirected aminations of unactivated C(sp 3 )-H bonds remains an outstanding challenge. Here, we report the origins of the reactivity and selectivity of a Cu-catalyzed C-H amidation of simple alkanes. Using a combination of experimental and computational mechanistic studies and energy decomposition techniques, we uncover a switch in mechanism from inner-sphere to outer-sphere coupling between alkyl radicals and the active Cu(II) catalyst with increasing substitution of the alkyl radical. The combination of computational predictions and detailed experimental validation shows that simultaneous minimization of both Cu-C covalency and alkyl radical size increases the rate of reductive elimination and that both strongly electron-donating and electron-withdrawing substituents on the catalyst accelerate the selectivity-determining C-N bond formation process as a result of a change in mechanism. These findings offer design principles for the development of improved catalyst scaffolds for radical C-H functionalization reactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2021

Density of Fe-Ni-C Liquids at High Pressures and Implications for Liquid Cores of Earth and the Moon

The presence of light elements in the metallic cores of the Earth, the Moon, and other rocky planetary bodies has been widely proposed. Carbon is among the top candidates in light of its high cosmic abundance, siderophile nature, and ubiquity in iron meteorites. It is, however, still controversial whether carbon-rich core compositional models can account for the seismic velocity observations within the Earth and lunar cores. In this paper we report the density and elasticity of Fe 90 Ni 10 -3 wt.% C and Fe 90 Ni 10 -5 wt.% C liquid alloys using synchrotron-based X-ray absorption experiments and first-principles molecular dynamics simulations. Our results show that alloying of 3 wt.% and 5 wt.% C lowers the density of Fe 90 Ni 10 liquid by ~2.9-3.1% at 2 GPa, and ~3.4-3.6% at 9 GPa. More intriguingly, our experiments and simulations both demonstrate that the bulk moduli of the Fe-Ni-C liquids are similar to or slightly higher than those of Fe-Ni liquids. Thus, the calculated compressional velocity ($v_p$) of Fe-Ni-C liquids are higher than that of pure Fe-Ni alloy, promoting carbon as a possible candidate to explain the elevated v p in the Earth's outer core. However, the values and slopes of both density and v p of the studied two Fe-Ni-C liquids do not match the outer core seismic models, suggesting that carbon may not be the sole principal light element in Earth's outer core. The high $v_p$ of Fe-Ni-C liquids does not match the presumptive $v_p$ of the lunar outer core well, indicating that carbon is less likely to be its dominant light element.

58 GEOSCIENCES↗