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DOE OSTI2020

Structure of the Polymer Backbones in polyMOF Materials

The molecular connectivity of polymer–metal–organic framework (polyMOF) hybrid materials was investigated using density functional theory calculations and solid-state NMR spectroscopy. The architectural constraints that dictate the formation of polyMOFs were assessed by examining poly(1,4-benzenedicarboxylic acid) (pbdc) polymers in two archetypical MOF lattices (UiO-66 and IRMOF-1). Modeling of the polyMOFs showed that in the IRMOF-1-type lattice, six, seven, and eight methylene (–CH 2 –) groups between 1,4-benzenedicarboxylate (terephthalate, bdc 2– ) units can be accommodated without significant distortions, while in the UiO-66-type lattice, an optimal spacing of seven methylene groups between bdc 2– units is needed to minimize strain. Solid-state NMR supports these predictions and reveals pronounced spectral differences for the same polymer in the two polyMOF lattices. With seven methylene groups, polyUiO-66-7a shows 7 ± 3% of uncoordinated terephthalate linkers, while these are undetectable (<4%) in the corresponding polyIRMOF-1-7a. Additionally, NMR-detected backbone mobility is significantly higher in the polyIRMOF-1-7a than in the corresponding polyUiO-66-7a, again indicative of taut chains in the latter.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2020

Electron Redistribution within the Nitrogenase Active Site FeMo-cofactor During Reductive Elimination of H2 to Achieve N=N Triple-Bond Activation

Nitrogen fixation by nitrogenase begins with accumulation of four reducing equivalents at the active-site FeMo-cofactor (FeMo-co), generating a state (denoted E4(4H)) with two [Fe-H-Fe] bridging hydrides. Recently, photolytic reductive elimination (re) of the E4(4H) hydrides showed that enzymatic re of E4(4H) hydride yields an H2-bound complex (E4(H2,2H)), in a process corresponding to a formal 2-electron reduction of the metal-ion core of FeMo-co. The resulting electron-density redistribution from Fe-H bonds to the metal ions themselves enables N2 to bind with concomitant H2 release, a process illuminated here by QM/MM molecular dynamics simulations. What is the nature of this redistribution? Although E4(H2,2H) hasn’t been trapped, cryogenic photolysis of E4(4H) provides a means to address this question. Photolysis of E4(4H) causes hydride-re with release of H2, generating doubly-reduced FeMo-co (denoted E4(2H)*), the extreme limit of the electron-density redistribution upon formation of E4(H2,2H). Here we examine the doubly-reduced FeMo-co core of the E4(2H)* limiting-state by 1H, 57Fe, and 95Mo ENDOR to illuminate the partial electron-density redistribution upon E4(H2,2H) formation during catalysis, complementing these results with corresponding DFT computations. Inferences from the E4(2H)* ENDOR results as extended by DFT computations include: (i) the Mo-site participates negligibly, and overall it is unlikely that Mo changes valency throughout the catalytic cycle; (ii) two distinctive E4(4H) 57Fe signals are suggested as associated with ‘anchors’ of one bridging hydride, two others with anchors of the second, with NBO-analysis identifying one anchor of each hydride as a major recipient of electrons released upon breaking Fe-H bonds.

Lukoyanov, Dmitriy↗

DOE OSTI2020

Generating Potent C–H PCET Donors: Ligand-Induced Fe-to-Ring Proton Migration from a Cp*Fe III –H Complex Demonstrates a Promising Strategy

Highly reactive organometallic species that mediate reductive proton-coupled electron transfer (PCET) reactions are an exciting area for development in catalysis, where a key objective focuses on tuning the reactivity of such species. Here, this work pursues ligand-induced activation of a stable organometallic complex toward PCET reactivity. This is studied via the conversion of a prototypical Cp*Fe III –H species, [Fe III (η 5 -Cp*)(dppe)H] + (Cp* = C 5 Me 5 –, dppe = 1,2-bis(diphenylphosphino)ethane), to a highly reactive, S = 1/2 ring-protonated endo-Cp*H–Fe relative, triggered by the addition of CO. Our assignment of the latter ring-protonated species contrasts with its previous reported formulation, which instead assigned it as a hypervalent 19-electron hydride, [Fe III (η 5 -Cp*)(dppe)(CO)H] + . Herein, pulse EPR spectroscopy ( 1,2 H HYSCORE, ENDOR) and X-ray crystallography, with corresponding DFT studies, cement its assignment as the ring-protonated isomer, [Fe I (endo-η 4 -Cp*H)(dppe)(CO)]+. A less sterically shielded and hence more reactive exo-isomer can be generated through oxidation of a stable Fe 0 (exo-η 4 -Cp*H)(dppe)(CO) precursor. Both endo- and exo-ring-protonated isomers are calculated to have an exceptionally low bond dissociation free energy (BDFE C–H ≈ 29 kcal mol –1 and 25 kcal mol –1 , respectively) cf. BDFE Fe–H of 56 kcal mol –1 for [Fe III (η 5 -Cp*)(dppe)H] + . These weak C–H bonds are shown to undergo proton-coupled electron transfer (PCET) to azobenzene to generate diphenylhydrazine and the corresponding closed-shell [Fe II (η 5 -Cp*)(dppe)CO] + byproduct.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2020

Substituent Effects on Exchange Coupling and Magnetic Relaxation in 2,2'-Bipyrimidine Radical-Bridged Dilanthanide Complexes

Systematic analysis of related compounds is crucial to the design of single-molecule magnets with improved properties, yet such studies on multinuclear lanthanide complexes with strong magnetic coupling remain rare. In this work, we present the synthesis and magnetic characterization of the series of radical-bridged dilanthanide complex salts [(Cp* 2 Ln) 2 (μ-5,5'-R 2 bpym)](BPh 4 ) (Ln = Gd, Dy; R = NMe 2 (1), OEt (2), Me (3), F (4); bpym = 2,2'-bipyrimidine). Modification of the substituent on the bridging 5,5'-R 2 bpym radical anion allows the magnetic exchange coupling constant, J Gd-rad , for the gadolinium compounds in this series to be tuned over a range from -2.7 cm -1 (1) to -11.1 cm -1 (4), with electron-withdrawing or -donating substituents increasing or decreasing the strength of exchange coupling, respectively. Modulation of the exchange coupling interaction has a significant impact on the magnetic relaxation dynamics of the single-molecule magnets 1-Dy through 4-Dy, where stronger J Gd-rad for the corresponding Gd 3+ compounds is associated with larger thermal barriers to magnetic relaxation ( U eff ), open magnetic hysteresis at higher temperatures, and slower magnetic relaxation rates for through-barrier processes. Further, we derive an empirical linear correlation between the experimental U eff values for 1-Dy through 4-Dy and the magnitude of J Gd-rad for the corresponding gadolinium derivatives that provides insight into the electronic structure of these complexes. This simple model applies to other organic radical-bridged dysprosium complexes in the literature, and it establishes clear design criteria for increasing magnetic operating temperatures in radical-bridged molecules.

36 MATERIALS SCIENCE↗

DOE OSTI2021

Redox-Induced Structural Reorganization Dictates Kinetics of Cobalt(III) Hydride Formation via Proton-Coupled Electron Transfer

Two-electron, one-proton reactions of a family of [CoCp(dxpe)(NCCH 3 )] 2+ complexes (Cp = cyclopentadienyl, dxpe = 1,2-bis(di(aryl/alkyl)phosphino)ethane) form the corresponding hydride species [HCoCp(dxpe)] + through a stepwise proton-coupled electron transfer process. For three [CoCp(dxpe)(NCCH 3 )] 2+ complexes (dxpe = dppe (1,2-bis(diphenylphosphino)ethane), depe (1,2-bis(diethylphosphino)ethane), and dcpe (1,2-bis(dicyclohexylphosphino)ethane)), peak shift analysis was employed to quantify apparent proton transfer rate constants from cyclic voltammograms recorded with acids ranging 22 pK a units. The apparent proton transfer rate constants correlate with the strength of the proton source for weak acids, but these apparent proton transfer rate constants curiously plateau (k pl ) as the reaction becomes increasingly exergonic. The absolute apparent proton transfer rate constants across both these regions correlate with the steric bulk of the chelating diphosphine ligand, with bulkier ligands leading to slower kinetics (k plateau,depe = 3.5 x 10 7 M -1 s -1 , k plateau,dppe = 1.7 x 10 7 M -1 s -1 , k plateau,dcpe = 7.1 x 10 4 M -1 s -1 ). Mechanistic studies were conducted to identify the cause of the aberrant $k_PT^{app}$–ΔpK a trends. When the deuterated acids are employed, deuterium incorporation in the Cp ring is observed, indicating protonation of the CoCp(dxpe) species to form the corresponding hydride proceeds via initial ligand protonation. Digital simulations of cyclic voltammograms show ligand loss accompanying initial reduction gates subsequent PCET activity at higher driving forces. Together, these experiments reveal the details of the reaction mechanism: reduction of the Co(III) species is followed by dissociation of the bound acetonitrile ligand, subsequent reduction of the unligated Co(II) species to form a Co(I) species is followed by protonation, which occurs at the Cp ring, followed by tautomerization to generate the stable Co(III)-hydride product [HCoCp(dxpe)] + . Analysis as a function of chelating disphosphine ligand, solvent, and acid strength reveals that the ligand dissociation equilibrium is directly influenced by the steric bulk of the phosphine ligands and gates protonation, giving rise to the plateau of apparent proton transfer rate constant with strong acids. The complexity of the reaction mechanism underpinning hydride formation, encompassing dynamic behavior of the entire ligand set, highlights the critical need to understand elementary reaction steps in proton-coupled electron transfer reactions.

14 SOLAR ENERGY↗

DOE OSTI2021

Self-Assembly of Metallo-Supramolecules with Dissymmetrical Ligands and Characterization by Scanning Tunneling Microscopy

Asymmetrical and dissymmetrical structures are widespread and play a critical role in nature and life systems. In the field of metallo-supramolecular assemblies, it is still in its infancy for constructing artificial architectures using dissymmetrical building blocks. Herein, we report the self-assembly of supramolecular systems based on two dissymmetrical double-layered ligands. With the aid of ultra-high-vacuum, low-temperature scanning tunneling microscopy (UHV-LT-STM), we were able to investigate four isomeric structures corresponding to four types of binding modes of ligand LA with two major conformations complexes A. The distribution of isomers measured by STM and total binding energy of each isomer obtained by density functional theory (DFT) calculations suggested that the most abundant isomer could be the most stable one with highest total binding energy. Lastly, through shortening the linker between inner and outer layers and the length of arms, the arrangement of dissymmetrical ligand LB could be controlled within one binding mode corresponding to the single conformation for complexes B.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2023

Controlling the Self-Assembly of DNA Origami Octahedra via Manipulation of Inter-Vertex Interactions

Recent studies have demonstrated novel strategies for the organization of nanomaterials into three-dimensional (3D) ordered arrays with prescribed lattice symmetries using DNA-based self-assembly strategies. In one approach, the nanomaterial is sequestered into DNA origami frames or “material voxels” and then coordinated into ordered arrays based on the voxel geometry and the corresponding directional interactions based on its valency. While the lattice symmetry is defined by the valency of the bonds, a larger-scale morphological development is affected by assembly processes and differences in energies of anisotropic bonds. To facilely model this assembly process, we investigate the self-assembly behavior of hard particles with six interacting vertices via theory and Monte Carlo simulations and exploration of corresponding experimental systems. We demonstrate that assemblies with different 3D crystalline morphologies, but the same lattice symmetry can be formed depending on the relative strength of vertex-to-vertex interactions in orthogonal directions. We observed three distinct assembly morphologies for such systems: cube-like, sheet-like, and cylinder-like. A simple analytical theory inspired by well-established ideas in the areas of protein crystallization, based on calculating the second virial coefficient of patchy hard spheres, captures the simulation results and thus represents a straightforward means of modeling this self-assembly process. To complement the theory and simulations, experimental studies were performed to investigate the assembly of octahedral DNA origami frames with varying binding energies at their vertices. In conclusion, x-ray scattering confirms the robustness of the formed nanoscale lattices for different binding energies, while both optical and electron microscopy imaging validated the theoretical predictions on the dependence of the distinct morphologies of assembled state on the interaction strengths in the three orthogonal directions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2025

Olefin Coupling Catalyzed by (Pybox)Os Complexes via Osmacyclopentane Intermediates: Comparison with Isoelectronic (Phebox)Ir

(Pybox)Os is found to catalyze alkene hydrovinylation, effecting the dimerization of ethylene, tail-to-tail coupling of propene and 1-butene, and cross-coupling of ethylene with higher α-olefins. This reactivity contrasts with the previously reported dehydrogenative coupling of ethylene to give butadiene catalyzed by the isoelectronic fragment (Phebox)Ir. The reaction mechanism was investigated through computational and experimental means. Both the Os- and Ir-catalyzed reactions proceed through a [2 + 2 + 1] cyclization of the corresponding bis-olefin complex to yield an experimentally observed metallacyclopentane intermediate. In both cases, the metallacyclopentane undergoes β- H elimination, via a dechelated κ 2 -pincer-ligated intermediate, to yield a σ−π-but-3-enyl hydride complex or derivative. Both the greater reactivity and the distinct chemoselectivity of the Os system relative to the Ir system are attributable to C−H reductive elimination by the σ−π-but-3-enyl hydride having a barrier for Os much lower than that for Ir. This lower barrier to C−H elimination for Os is unexpected given that the thermodynamic driving force for elimination is much less for Os than for Ir. Computational studies of model complexes were conducted, comparing (Pybox)Os(L)(CH 3 )(H) with the isoelectronic (Phebox)Ir(L)(CH 3 )(H). The results indicate that the more facile kinetics with Os relative to Ir may be general for C−H elimination from six-coordinate d 6 complexes of the two metals, as well as for the microscopic reverse, i.e., C−H addition to the corresponding four-coordinate d 8 species.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2020

Efficient Nighttime Biogenic SOA Formation in a Polluted Residual Layer

Abstract Organic nitrates formed from nighttime reaction between anthropogenic nitrate radicals (NO3) and biogenic volatile organic compounds (BVOCs) are potentially an important but highly uncertain source of secondary organic aerosol (SOA). Here we report on the enhanced nighttime biogenic SOA formation observed in a polluted residual layer over Sacramento, California, the morning of 15 June 2010 during the Carbonaceous Aerosols and Radiative Effects Study (CARES). Trajectory analysis showed that the residual layer air, containing trace amounts of isoprene and monoterpenes left over after nighttime oxidation, was influenced by the San Francisco Bay Area emissions the previous evening. The residual layer aerosol was also enriched in nitrate, with about 64% of it estimated to be in the form of organic nitrates. The nitrate:organic mass ratio of the SOA was about 0.47±0.044, which corresponds to the range typically found in isoprene mononitrates. Assuming the SOA was composed of organic mononitrates, its nominal molecular weight was estimated at 186±11 g mol-1, consistent with the highly functionalized isoprene hydroxynitrates that have been observed in the particle phase in the southeast United States. Overall, our findings show that the efficiency of nighttime biogenic SOA formation, expressed as the change in organic aerosol mass relative to carbon monoxide (?OA/?CO), was about 100 µg m-3 ppmv, which falls in the range 77-157 µg m-3 ppmv previously estimated for enhanced daytime SOA formation from mixed anthropogenic and biogenic emissions during CARES.

Zaveri, Rahul A.↗

DOE OSTI2020

Uncertainties in turbulent statistics and fluxes of CO2 associated with density effect corrections

Density effect corrections (DEC) are applied to adjust raw CO2 fluxes measured by eddy covariance (EC) systems with open-path gas analyzers. DEC is also required for adjusting the measured CO2 concentration fluctuations to obtain the adjusted CO2 for analyzing turbulent statistics or quantifying fluxes. However, our data show that the power spectra of the DEC-adjusted CO2 are distorted in the high frequency range, as compared with the corresponding spectra of temperature and water vapor density. This contradicts the similarity behavior of scalars, as suggested by Monin-Obukhov similarity theory. It is demonstrated that such a distortion is caused by the DEC-induced spikes in the DEC-adjusted CO2, altering turbulent statistics of CO2 and scalar similarity between CO2 and other scalars. Our results suggest that CO2 fluxes are overestimated by applying DEC especially under high Bowen ratio conditions, potentially leading to substantial uncertainties in long-term ecosystem carbon exchange in dry regions.

Gao, Zhongming↗

DOE OSTI2021

The Leading Modes of Asian Summer Monsoon Variability as Pulses of Atmospheric Energy Flow

Monsoon rainfall anomalies are often organized into dynamical modes that are more predictable than rainfall at specific locations. Here a linear response function (LRF) is constructed to extract the neutral modes (NM) of the dynamical atmospheric system and their optimal forcing that govern precipitation variability, providing a dynamical underpinning for the empirically derived, recurrent rainfall patterns. The leading mode (NM1) features a shift in the Atlantic ITCZ, a drying over the Indian Ocean and Indian subcontinent, and a “South-Flood-North Drought (SFND)” pattern over eastern China, a pattern inferable from changes in the atmospheric energy flow forced by the corresponding optimal forcing and further enhanced by the water vapor and cloud feedbacks. Moreover, the slow evolving component of the NM1 in response to CO2 forcing can be skillfully predicted by running the ocean heat uptake through the LRF, implicating a deterministic ocean dynamic source for the NM1-like trend under climate warming.

monsoon mode of variability, EBM, climate change, ↗

DOE OSTI2021

Understanding the Cold Season Arctic Surface Warming Trend in Recent Decades

Abstract Whether sea‐ice loss or lapse‐rate feedback dominates the Arctic amplification (AA) remains an open question. Analysis of data sets based upon observations reveals a 1.11 K per decade surface warming trend in the Arctic (70°–90°N) during 1979–2020 cold season (October–February) that is five times higher than the corresponding global mean. Based on surface energy budget analysis, we show that the largest contribution (∼82%) to this cold season warming trend is attributed to changes in clear‐sky downward longwave radiation. In contrast to that in Arctic summer and over tropics, a reduction in lower‐tropospheric inversions plays a unique role in explaining the reduction of the downward longwave radiation associated with atmospheric nonuniform temperature and corresponding moisture changes. Our analyses also suggest that Arctic lower‐tropospheric stability should be considered in conjunction with sea‐ice decline during the preceding warm season to explain AA.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2023

Hybrid Simulation of Proton Cyclotron Waves Upstream of Mars Generated by Pickup Ion Beam Distribution

Linear instability analysis as well as a corresponding two‐dimensional hybrid simulation are performed to examine the excitation of the proton cyclotron waves observed upstream of Mars. The waves are believed to be excited by the pickup ions produced from the ionization of the Martian hydrogen exosphere. And previous statistical analysis of wave observations suggested that the waves are mostly related to pickup ion beam velocity distributions. While earlier linear instability analysis of pickup ion beam distributions has mainly been focused on the parallel unstable modes, our analysis reveals that the maximum growth rate occurs at very oblique propagation. The corresponding hybrid simulation confirms the linear analysis results and further demonstrates that the pickup ions are scattered toward an isotropic shell velocity distribution by the waves excited. Interestingly, the waves at oblique propagation gradually damp out and the system is eventually dominated by waves of quasi‐parallel propagation.

79 ASTRONOMY AND ASTROPHYSICS↗

DOE OSTI2023

The Thermal Plumbing System of Stromboli Volcano, Aeolian Islands (Italy) Inferred From Electrical Conductivity and Induced Polarization Tomography

Abstract We performed the first 3D island‐scale tomography of the electrical conductivity of Stromboli volcano (Aeolian Islands, Italy) using 2D acquisition lines (37.2 km) and a total of 18,880 measurements and 2,402 unique electrode locations. This 3D data set was inverted using a Gauss‐Newton algorithm, parallel‐processing on an unstructured tetrahedral mesh containing 678,420 finite‐element nodes and 3,580,145 elements to account for the topography of the volcanic island. The tomogram exhibits a conductive body (10 −2 –1.0 S m −1 ) consistent with the location of CO 2 and temperature anomalies observed at the ground surface. It corresponds to the hydrothermal system with high electrical conductivity associated with alteration. In order to confirm this interpretation, a 2.5D large‐scale induced polarization tomography was performed crossing the volcano. The joint interpretation of the conductivity and normalized chargeability is done with a petrophysical model previously tested and verified at both shield‐ and strato‐volcanoes. This model implies that alteration (through the effect of the cation exchange capacity associated with clay minerals and zeolites) plays a strong role in both controlling the electrical conductivity and normalized chargeability at Stromboli volcano. A temperature tomogram, derived from the geoelectrical measurements, is consistent with surface temperature anomalies and the Very Long Period (VLP) seismicity related to the mild‐explosive activity. This survey displays at 600 m a.s.l. a lateral shift in the highest temperature location, also corresponding to the source of VLP seismicity. Structural boundaries have a major role in the hottest hydrothermal fluids rising below the active crater terrace of Stromboli volcano.

58 GEOSCIENCES↗

DOE OSTI2024

Extreme Precipitation Over the Southern Slope of the Tibetan Plateau and the Associated Atmospheric Circulation Anomalies

The southern slope of the Tibetan Plateau (SSTP) is one of the rainiest regions in the world where geological hazards caused by extreme precipitation often occur. This study investigates the characteristics and mechanisms of extreme precipitation over SSTP from June to September during 2001–2020 using Global Precipitation Measurement satellite observation. The extreme precipitation days are defined as the days with top 5% of regional-mean daily precipitation over SSTP in this period, which has an average precipitation of 27.2 mm/d. Averaging over the extreme precipitation days, precipitation peaks at an altitude of about 300 m, coinciding with the climatological maximum precipitation, but with a much larger value of 37.2 mm/d than the climatology of 11.9 mm/d. Composite analysis of circulations on extreme days reveals significant circulation anomalies in both the lower and upper troposphere. Specifically, the lower-tropospheric circulations are characterized by significant westerly anomalies over northern India, and the upper-tropospheric circulations are characterized by northerly anomalies over the central Tibetan Plateau, which are statistically independent. The lower-tropospheric westerly anomalies blowing toward SSTP are blocked by the topography, favoring extreme precipitation over SSTP. The upper-tropospheric northerly anomalies, on the other hand, correspond to anomalous northeasterlies north of SSTP in the middle troposphere and southeasterlies to the south in the lower troposphere, and the convergence of these circulation anomalies favors extreme precipitation over SSTP. Lastly, the lower-tropospheric westerly and upper-tropospheric northerly anomalies, respectively, correspond to less precipitation over the South Asian monsoon region and the Tibetan Plateau.

Extreme precipitation, Tibetan Plateau↗

DOE OSTI2025

A Novel Thermodynamical Predictor of Tropical High‐Cloud Area Coverage: Estimated Anvil‐Outflow Stability

The stability at the lapse-rate tropopause (LRT) was previously defined as the upper-tropospheric stability (UTS and SUT) but might underestimate the stability control on high-level clouds, since there is little direct connection between convective processes and the thermal stratification at the LRT. Here, a novel estimated anvil-outflow stability (EAS) based on the minimum stability in the upper troposphere is proposed. At the Manus site, the results show that small and large values of the LRT-based UTS and SUT both correspond to strong divergence and frequent occurrence of high-level ice clouds. In contrast, smaller EAS corresponds to stronger convective outflows to produce likely more high-level ice clouds, with a strong negative correlation. In tropics, EAS better explains the geographic distribution of high-level cloud coverage (HCC) and its temporal variations than UTS and SUT. With a strong linear correlation, EAS is likely a simple useful predictor of HCC.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2022

Chemolithoautotroph distributions across the subsurface of a convergent margin

Subducting oceanic crusts release fluids rich in biologically relevant compounds into the overriding plate, fueling subsurface chemolithoautotrophic ecosystems. To understand the impact of subsurface geochemistry on microbial communities, we collected fluid and sediments from 14 natural springs across a ~200 km transect across the Costa Rican convergent margin and performed shotgun metagenomics. The resulting 404 metagenome-assembled genomes (MAGs) cluster into geologically distinct regions based on MAG abundance patterns: outer forearc-only (25% of total relative abundance), forearc/arc-only (38% of total relative abundance), and delocalized (37% of total relative abundance) clusters. In the outer forearc, Thermodesulfovibrionia, Candidatus Bipolaricaulia, and Firmicutes have hydrogenotrophic sulfate reduction and Wood-Ljungdahl (WL) carbon fixation pathways. In the forearc/arc, Anaerolineae, Ca. Bipolaricaulia, and Thermodesulfovibrionia have sulfur oxidation, nitrogen cycling, microaerophilic respiration, and WL, while Aquificae have aerobic sulfur oxidation and reverse tricarboxylic acid carbon fixation pathway. Transformation-based canonical correspondence analysis shows that MAG distribution corresponds to concentrations of aluminum, iron, nickel, dissolved inorganic carbon, and phosphate. While delocalized MAGs appear surface-derived, the subsurface chemolithoautotrophic, metabolic, and taxonomic landscape varies by the availability of minerals/metals and volcanically derived inorganic carbon. Furthermore, the WL pathway persists across all samples, suggesting that this versatile, energy-efficient carbon fixation pathway helps shape convergent margin subsurface ecosystems.

59 BASIC BIOLOGICAL SCIENCES↗

DOE OSTI2024

The role of charge in microdroplet redox chemistry

In charged water microdroplets, which occur in nature or in the lab upon ultrasonication or in electrospray processes, the thermodynamics for reactive chemistry can be dramatically altered relative to the bulk phase. Here, we provide a theoretical basis for the observation of accelerated chemistry by simulating water droplets of increasing charge imbalance to create redox agents such as hydroxyl and hydrogen radicals and solvated electrons. We compute the hydration enthalpy of OH - and H + that controls the electron transfer process, and the corresponding changes in vertical ionization energy and vertical electron affinity of the ions, to create OH • and H • reactive species. We find that at ~ 20 - 50% of the Rayleigh limit of droplet charge the hydration enthalpy of both OH - and H + have decreased by >50 kcal/mol such that electron transfer becomes thermodynamically favorable, in correspondence with the more favorable vertical electron affinity of H + and the lowered vertical ionization energy of OH - . We provide scaling arguments that show that the nanoscale calculations and conclusions extend to the experimental microdroplet length scale. The relevance of the droplet charge for chemical reactivity is illustrated for the formation of H 2 O 2 , and has clear implications for other redox reactions observed to occur with enhanced rates in microdroplets.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗