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DOE OSTI2025

Impact of nitrogen molecular breakup on divertor conditions in JET L-mode plasmas using SOLPS-ITER

SOLPS-ITER simulations of nitrogen-seeded, low-confinement mode plasmas in the Joint European Torus (JET) predict that the electron temperature in the low-field side (LFS) divertor leg is reduced locally by up to an order of magnitude when nitrogen is assumed to recycle as molecules (N 2 ) instead of atoms using a fixed nitrogen injection rate. The LFS divertor temperature reduction under the assumption of molecular recycling occurs due to a three-step mechanism: (1) the plasma penetration of nitrogen atoms is increased due to the strong triple bond of the N 2 molecule and the kinetic energy release in the dissociation event, both mechanisms contributing equally, (2) the abundance of (particularly multiply-charged) nitrogen ions in the divertor is increased and (3) the electron temperature is reduced due to the increase in radiation (by up to a factor of 4) from nitrogen ions. Setting the volume-integrated nitrogen radiated power to a constant value (0.6 MW) instead of the nitrogen injection rate, SOLPS-ITER predicts under the molecular nitrogen recycling assumption that the peak line-integrated N II, N III and N IV intensities in the LFS divertor are approximately within 15%, 35% and 5%, respectively, of the reference atomic nitrogen recycling case. The predicted peak N II, N III and N IV intensities under either assumption are within 30%, 65% and 5%, respectively, of measurements using the vertically viewing mirror-link divertor spectrometer (Meigs et al., 2010) in nitrogen-seeded JET L-mode plasmas (Lomanowski et al., 2019). ERO2.0 simulations using a constant nitrogen seeding rate on static background plasma solutions from EDGE2D-EIRENE (previously presented in Mäenpää et al., (2022), revised here to include fast reflections) predict that N II to N IV line emission is increased by 20% to 30% when nitrogen is assumed to recycle as molecules, demonstrating the importance of considering the effect of molecular dissociation reactions on the divertor plasma in a self-consistent manner.

Divertor↗

DOE OSTI2024

Electric field enhanced diffusion welding of alloy 617: Microstructural characteristics and mechanical properties

This study investigated the microstructural characteristics and mechanical behavior of diffusion welded nickel-based Alloy 617 obtained by electric field-assisted sintering (EFAS) using various parameters. The interfacial microstructure exhibited different characteristics including good grain boundary (GB) migration across the interface in the samples diffusion-welded at 1100 °C and a flat interface in the samples joined at 1000 °C and 1050 °C. The interface consisted of fine Al 2 O 3 oxides, while precipitation of interfacial M 23 C 6 carbides was not observed. Grain boundaries migrated across the Al 2 O 3 oxides, leaving these oxides within the grains. Graded grain size was observed, with grain coarsening being more significant near the sample surface due to the temperature gradient induced by EFAS. Tensile testing revealed that the specimens fractured in the matrix away from the interface, indicting strong diffusion-welded joints. Further, the peak tensile strength of 807 MPa was obtained in the samples welded at 1000 °C due to minimal grain growth. The materials obtained at 1100 °C exhibited reduced tensile strength but improved ductility. Strain maps revealed by digital image correlation showed alternating high and low strain segments in the samples produced at 1000 °C and 1050 °C, indicating that the flat interfaces with no GB migration were less ductile compared to the matrix. A greater strain uniformity was observed along the bond interfaces with improved GB migration. The hardness reduced near the sample surfaces due to enlarged grains induced by temperature gradient. This study demonstrates that GB migration and enhanced mechanical strength can be achieved in diffusion-welded Alloy 617.

36 MATERIALS SCIENCE↗

DOE OSTI2024

TOI-2374 b and TOI-3071 b: two metal-rich sub-Saturns well within the Neptunian desert

ABSTRACT We report the discovery of two transiting planets detected by the Transiting Exoplanet Survey Satellite (TESS), TOI-2374 b and TOI-3071 b, orbiting a K5V and an F8V star, respectively, with periods of 4.31 and 1.27 d, respectively. We confirm and characterize these two planets with a variety of ground-based and follow-up observations, including photometry, precise radial velocity monitoring and high-resolution imaging. The planetary and orbital parameters were derived from a joint analysis of the radial velocities and photometric data. We found that the two planets have masses of (57 ± 4) M⊕ or (0.18 ± 0.01) MJ, and (68 ± 4) M⊕ or (0.21 ± 0.01) MJ, respectively, and they have radii of (6.8 ± 0.3) R⊕ or (0.61 ± 0.03) RJ and (7.2 ± 0.5) R⊕ or (0.64 ± 0.05) RJ, respectively. These parameters correspond to sub-Saturns within the Neptunian desert, both planets being hot and highly irradiated, with Teq ≈ 745 K and Teq ≈ 1812 K, respectively, assuming a Bond albedo of 0.5. TOI-3071 b has the hottest equilibrium temperature of all known planets with masses between 10 and 300 M⊕ and radii less than 1.5 RJ. By applying gas giant evolution models we found that both planets, especially TOI-3071 b, are very metal-rich. This challenges standard formation models which generally predict lower heavy-element masses for planets with similar characteristics. We studied the evolution of the planets’ atmospheres under photoevaporation and concluded that both are stable against evaporation due to their large masses and likely high metallicities in their gaseous envelopes.

Hacker, Alejandro (ORCID:0009000994520181)↗

DOE OSTI2022

Functionalization of Electrodes with Tunable [EMIM] x [Cl] x +1 – Ionic Liquid Clusters for Electrochemical Separations

Functionalization of electrodes with clusters of hydrophobic molecules may improve the energy efficiency and selectivity of electrochemical separations by modulating the desolvation process occurring at the interface. Ionic liquids (IL), which have a broad range of compositions and properties, are potential candidates for controlling the transport, desolvation, and adsorption of target ions at electrochemical interfaces. We report a joint experimental and theoretical investigation of the structure, stability, and selective adsorption properties of the IL clusters 1-ethyl-3-methylimidazolium chloride [EMIM] x [Cl] x+1 - (x = 1 – 10) and demonstrate their ability to adsorb and separate ions from solution. The structure and stability of the IL clusters are determined experimentally using high-mass-resolution electrospray ionization mass spectrometry, collision-induced dissociation, and negative ion photoelectron spectroscopy. Global optimization theory and ab initio molecular dynamics simulations provide molecular-level insight into the bonding and structural fluxionality of these species. Ion soft landing is used to selectively functionalize the surface of highly oriented pyrolytic graphite (HOPG) working electrodes with [EMIM] 1 [Cl] 2 - , [EMIM] 3 [Cl] 4 - , and [EMIM] 5 [Cl] 6 - clusters. Kelvin probe microscopy provides insight into the relative stability of the clusters on HOPG and their effect on the work function of IL-functionalized electrodes. Cyclic voltammetry measurements reveal irreversible adsorption of Fe(CN) 6 4-/3- anions during redox cycling, while electrochemical impedance spectroscopy indicates a substantial decrease in the electron transfer resistance of the IL-functionalized electrodes due to adsorption of Fe(CN) 6 4-/3- . Overall, our findings demonstrate that IL clusters with different size and stoichiometry may be used to increase the efficiency of electrochemical separations, opening new horizons in selective electrode functionalization.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2021

Effect of static local distortions vs. dynamic motions on the stability and band gaps of cubic oxide and halide perovskites

Ternary ABX 3 perovskites made of corner-sharing BX 6 octahedra have long featured prominently in solid-state chemistry and condensed matter physics. Still, the joint understanding of their two main subgroups—halides and oxides—has not been fully developed. Indeed, unlike the case in simpler compounds having a single, robust repeated motif (“monomorphous”), certain cubic perovskites can manifest a non-thermal (= intrinsic) distribution of local motifs (“polymorphous networks”). Such static deformations can include positional degrees of freedom (e.g., atomic displacements and octahedral tilting) or magnetic moment degrees of freedom in paramagnets. Unlike thermal motion, such static distortions do not time-average to zero, being an expression of the intrinsic symmetry breaking preference of the chemical bonding. Here, the present study compares electronic structure features of oxide and halide perovskites starting from the static polymorphous distribution of motifs described by Density Functional Theory (DFT) minimization of the internal energy, continuing to finite temperature thermal disorder modeled via finite temperature DFT molecular dynamics. We find that (i) different oxide vs. halide ABX 3 compounds adopt different energy-lowering symmetry-breaking modes. The calculated pair distribution function (PDF) of SrTiO 3 from the first-principles agrees with recently measured PDF. (ii) In both oxides and halides, such static distortions lead to band gap blueshifts with respect to undistorted cubic Pm-3m structure. (iii) For oxide perovskites, high-temperature molecular dynamics simulations initiated from the statically distorted polymorphous structures reveal that the thermally-induced distortions can lead to a band gap redshift. (iv) In contrast, for cubic halide perovskite CsPbI 3 , both the intrinsic distortions and the thermal distortions contribute in tandem to band gap blueshift, the former, intrinsic effect being dominant. (v) In the oxide SrTiO 3 and CaTiO 3 (but not in halide) perovskites, octahedral tilting leads to the emergence of a distinct Γ–Γ direct band gap component as a secondary valley minimum to the well-known indirect R–Γ gap. Understanding such intrinsic vs. thermal effects on oxide vs. halide perovskites holds the potential for designing target electronic properties.

36 MATERIALS SCIENCE↗

DOE OSTI2025

Resolving the Solvation Structure and Transport Properties of Aqueous Zinc Electrolytes from Salt-in-Water to Water-in-Salt Using Neural Network Potential

Zn Cl 2 solutions are promising electrolytes for aqueous zinc-ion batteries. Here, we report a joint computational and experimental study of the structural and dynamic properties of aqueous Zn Cl 2 electrolytes with concentrations ranging from salt-in-water to water-in-salt (WIS). By developing a neural network potential (NNP) model, we perform molecular dynamics (MD) simulations with accuracy but at much larger lengths and longer timescales. The NNP predicted structures are validated by the structure factors measured by X-ray total scattering experiments. The MD trajectories provide a comprehensive and quantitative picture of the Zn 2 + solvation shell structures. Additionally, we find that the O − H covalent bonds in water are strengthened with increasing salt concentration, thus expanding the electrochemical stability window of aqueous electrolytes. In terms of dynamic properties, the calculated and experimentally measured conductivities are in good agreement. Through the analysis of the calculated cation transference number, we propose a three-stage charge carrier transport mechanism with increasing concentration: independent ion transport, strongly correlated ion transport, and small positive charge carrier diffusion through negatively charged polymeric clusters. Our study provides fundamental atomic scale insights into the structure and transport properties of the Zn Cl 2 electrolyte that can aid the optimization and development of WIS electrolytes. Published by the American Physical Society 2025

25 ENERGY STORAGE↗

DOE OSTI2025

Resonant inelastic X-ray scattering tools to count 5 $f$ electrons of actinides and probe bond covalency

The actinides possess a complex electronic structure, making their chemical and physical properties among the least understood in the periodic table. Advanced spectroscopic tools, able to obtain deep insights into the electronic structure and binding properties of the actinides, are highly desirable. Here, we introduce two sensitive spectroscopic tools: one determines the number of localized 5f electrons on an actinide atom, and another assesses the covalent character of actinide-ligand bonding. Both tools are based on the multiplet structure present in actinide M 4 edge core-to-core resonant inelastic X-ray scattering (CC-RIXS) maps. The spectral intensity of different many-body final-state multiplets directly depends on the local many-electron ground-state symmetry including the local 5 f spin configuration. By comparing U M 4 edge CC-RIXS data for 21 U, Np, Pu and Am compounds, we demonstrate the ability to compare the number of localized 5 f electrons and bond covalency across the actinide series.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

DOE OSTI2023

Unifying principles for catalytic hydrotreating processes (Final Technical Report)

This project builds on the hypothesis that the hydrotreating processes for the removal of oxygen and sulfur are fundamentally similar at the atomic-scale and existing knowledge from the treatment of petroleum derived feedstock can be leveraged for the design of novel catalysts for the upgrade of bio-oil. We tested this hypothesis by comparing computed potential energy diagrams for hydrodesulfurization (HDS) of thiophene over MoS 2 with hydrodeoxygenation (HDO) of furan over MoO 3 and concluded that certain aspects, such as catalyst promotion with transition metals, are valid strategies for both reactions. On the other hand, we also noticed significant differences in the mechanism for hydrogen (H 2 ) activation, which requires sites with metallic character. While MoS 2 is known to have metallic edge states that can catalyze H 2 dissociation, this elementary step is prohibitively slow on defect-free oxides. Only in the presence of vacancies or by creating metal/oxide interfaces can efficient H 2 activation sites during HDO be formed. The need for bifunctional catalyst when it comes to efficient and selective HDO or dehydrogenation reactions was further corroborated in joint experimental and theoretical studies of the Guerbet reaction for the coupling of biomass derived oxygenates over PdCu alloys, nitrate reduction over In-promoted Pd nanoparticles, and ethylene dehydroaromatization over Ga-exchanged ZSM-5 zeolites. All of these catalytic systems have in common that catalytic sites with distinct functional requirements are needed to create a working catalyst. Detailed computational studies were carried out for HDO of m -cresol and phenol on Ru-modified TiO 2 surfaces, which allowed us to attribute catalytic activity to the metal/oxide interface. A surprising finding was that heterolytic cleavage of the H-H bond across the Ru/TiO 2 interface was critically important, despite lower barriers for homolytic H 2 activation on Ru metal. The explanation lies in the high barriers for hydrogen spillover from Ru to TiO 2 , which becomes unnecessary in the heterolytic activation pathway. Moreover, we also reported that proton transfer steps between metal and oxide sites are mediated by weakly adsorbed surface water. During attempts to develop and validate a kinetic Monte Carlo (kMC) model for HDO reactions at the Ru/TiO 2 interface, it became clear that lateral interactions are paramount to describe realistic surface chemistry and without these interactions, the reduction and hydroxylation behavior from our simulations was inconsistent with reported experiments. To assess the importance of lateral interactions in popular computational catalyst design strategies relying on the identification of reactivity descriptors, which can be used along with Brønsted–Evans–Polanyi (BEP) and scaling relations as input to a microkinetic model (MKM) to make predictions for activity or selectivity trends, we compared predicted trends with those obtained from descriptor-based kMC models. We critically evaluated the benefits of kMC over MKM in terms of trend predictions and computational cost when using only a small set of input parameters. After confirming that in the absence of lateral interactions the kMC and MKM approaches yield identical trends and mechanistic information, we observed substantial differences between the two kinetic models when lateral interactions were introduced. The mean-field implementation applies coverage corrections directly to the descriptors, causing an artificial overprediction of the activity of strongly binding metals. In contrast, the cluster expansion in kMC implementation can differentiate among the highly active metals but it is very sensitive to the set of included interaction parameters. Considering that computational screening relies on a minimal set of descriptors, for which MKM makes reasonable trend predictions at a ca. three orders of magnitude lower computational cost than kMC, we concluded that the MKM approach does provide an overall better entry point for computational catalyst design. Overall, this project has led to 11 peer-reviewed publications, and their scientific is impact is well illustrated by their combined 702 citations.

08 HYDROGEN↗

DOE OSTI2023

Bond-dependent anisotropy and magnon decay in cobalt-based Kitaev triangular antiferromagnet

Following tremendous success of the graphene-derived fundamental and applied research, the magnetic van der Waals materials that can be cleaved into monolayer two-dimensional atomic crystals have emerged as a new platform in the studies of low-dimensional physics and in the design of artificial heterostructures with novel properties. Because of that, the family of dihalides and trihalides of the 3d transition group receive a strong renewed interest. Together with our experimental collaborators, we have investigated the novel dynamical properties of one of such promising material CoI 2 , and demonstrated that spin excitations in it are prone to substantial breakdown and complex level repulsion, the important quantum effects whose theoretical understanding has been significantly advanced by our group in the last two decades. Both phenomena are dramatically revealed by experiments and verified by the theory in our joint study, published in Nature Physics. Altogether, our results pave the way toward a new research direction for the magnetic van der Waals materials.

36 MATERIALS SCIENCE↗

DOE OSTI2025

Analysis of Polarized Dust Emission Using Data from the First Flight of SPIDER

Using data from the first flight of Spider and from the Planck High Frequency Instrument, we probe the properties of polarized emission from interstellar dust in the Spider observing region. Component-separation algorithms operating in both the spatial and harmonic domains are applied to probe their consistency and to quantify modeling errors associated with their assumptions. Analyses of diffuse Galactic dust emission spanning the full Spider region demonstrate (i) a spectral energy distribution that is broadly consistent with a modified-blackbody (MBB) model with a spectral index of β d = 1.45 ± 0.05 (1.47 ± 0.06) for E (B)-mode polarization, slightly lower than that reported by Planck for the full sky; (ii) an angular power spectrum broadly consistent with a power law; and (iii) no significant detection of line-of-sight polarization decorrelation. Tests of several modeling uncertainties find only a modest impact (~10% in σ r ) on Spider's sensitivity to the cosmological tensor-to-scalar ratio. The size of the Spider region further allows for a statistically meaningful analysis of the variation in foreground properties within it. Assuming a fixed dust temperature T d = 19.6 K, an analysis of two independent subregions of that field results in inferred values of β d = 1.52 ± 0.06 and β d = 1.09 ± 0.09, which are inconsistent at the 3.9σ level. Furthermore, a joint analysis of Spider and Planck 217 and 353 GHz data within one subregion is inconsistent with a simple MBB at more than 3σ, assuming a common morphology of polarized dust emission over the full range of frequencies. This evidence of variation may inform the component-separation approaches of future cosmic microwave background polarization experiments.

79 ASTRONOMY AND ASTROPHYSICS↗

DOE OSTI2020

Planck 2018 results - VIII. Gravitational lensing

We present measurements of the cosmic microwave background (CMB) lensing potential using the final Planck 2018 temperature and polarization data. Using polarization maps filtered to account for the noise anisotropy, we increase the significance of the detection of lensing in the polarization maps from 5σ to 9σ. Combined with temperature, lensing is detected at 40σ. We present an extensive set of tests of the robustness of the lensing-potential power spectrum, and construct a minimum-variance estimator likelihood over lensing multipoles 8 ≤ L ≤ 400 (extending the range to lower L compared to 2015), which we use to constrain cosmological parameters. We find good consistency between lensing constraints and the results from the Planck CMB power spectra within the ΛCDM model. Combined with baryon density and other weak priors, the lensing analysis alone constrains σ 8 Ωm 0.25 = 0.589 ± 0.020 (1σ errors). Also combining with baryon acoustic oscillation data, we find tight individual parameter constraints, σ8 = 0.811 ± 0.019, H0 = 67.9-1.3+1.2 km s -1 Mpc -1 , and Ω m = 0.303 -0.018 +0.016 . Combining with Planck CMB power spectrum data, we measure σ 8 to better than 1% precision, finding σ 8 = 0.811 ± 0.006. CMB lensing reconstruction data are complementary to galaxy lensing data at lower redshift, having a different degeneracy direction in σ 8 - Ω m space; we find consistency with the lensing results from the Dark Energy Survey, and give combined lensing-only parameter constraints that are tighter than joint results using galaxy clustering. Using the Planck cosmic infrared background (CIB) maps as an additional tracer of high-redshift matter, we make a combined Planck-only estimate of the lensing potential over 60% of the sky with considerably more small-scale signal. We additionally demonstrate delensing of the Planck power spectra using the joint and individual lensing potential estimates, detecting a maximum removal of 40% of the lensing-induced power in all spectra. The improvement in the sharpening of the acoustic peaks by including both CIB and the quadratic lensing reconstruction is detected at high significance.

79 ASTRONOMY AND ASTROPHYSICS↗

DOE OSTI2026

The ionomer as an oxygen evolution reaction promoter: piperidinium’s impact on mechanistic pathways on NiO, IrO 2 , and Fe–NiO

The commercial viability of anion exchange membrane (AEM) electrolysis requires optimization of various stack components, with specific catalyst-ionomer combinations often yielding higher current densities, lowered Tafel slopes, and improved mass activity. In this joint theoretical-experimental study, theoretical calculations detail the impact of Versogen’s piperidinium functional group on the complex, kinetically limiting oxygen evolution reaction, finding that the functional group can act as a promoter of specific steps (O*/O 2 * formation; H 2 O/O 2 desorption with reaction enthalpies ranging between 0.2–0.6 eV at higher coverages of O x H y intermediates) on NiO and NiFeO x catalysts. In particular, Fe sites on the NiFeO x catalyst facilitate concerted mechanisms of O*/O 2 * formation and H 2 O desorption with a low enthalpy of 0.5 eV; O 2 desorption alone requires only 0.3 eV. In contrast, Versogen-IrO 2 results in stronger Ir–O bonds, where the enthalpies for bond breaking (Ir–OH 2 and Ir–O 2 ) are considerably higher (1.4 eV and 1.6 eV, respectively). Rotating disk electrode studies utilized commercially available NiO and IrO 2 and synthesized 7.5 wt % Fe in NiFeO x catalysts in combination with Versogen, a common AEM ionomer, and Nafion, an alternative binder. Electrochemical testing validated the impact of these mechanistic changes on ionomer-catalyst combinations, finding that Versogen particularly activates NiO and NiFeO x compared to IrO 2 . Following a 13.5 h hold at 1.8 V, mass activities and Tafel slopes improved to 34 ± 13 A g −1 and 79 ± 2 mV dec −1 (NiO) and 82 ± 4.9 A g −1 and 72 ± 2 mV dec −1 (NiFeO x ). In contrast, Versogen-IrO 2 only reached 17 ± 2.9 A g −1 and 81 ± 3 mV dec −1 . Optimization of the ionomer-catalyst can yield significant increases in performance from initial activity and after an electrochemical conditioning procedure: this enhancement to the mass activity resulted in a 200.9 ± 106.1% improvement for Versogen-NiFeO x and 1284.2 ± 260.5% for Versogen-NiO. In contrast, Nafion-NiFeO x and -NiO offered moderate improvements of 39.1 ± 30.5% and 120.9 ± 59.1%, respectively.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2025

Cosmological constraints from the cross-correlation of DESI Luminous Red Galaxies with CMB lensing from Planck PR4 and ACT DR6

Here, we infer the growth of large scale structure over the redshift range 0.4 ≲ z ≲ 1 from the cross-correlation of spectroscopically calibrated Luminous Red Galaxies (LRGs) selected from the Dark Energy Spectroscopic Instrument (DESI) legacy imaging survey with CMB lensing maps reconstructed from the latest Planck and ACT data. We adopt a hybrid effective field theory (HEFT) model that robustly regulates the cosmological information obtainable from smaller scales, such that our cosmological constraints are reliably derived from the (predominantly) linear regime. We perform an extensive set of bandpower- and parameter-level systematics checks to ensure the robustness of our results and to characterize the uniformity of the LRG sample. We demonstrate that our results are stable to a wide range of modeling assumptions, finding excellent agreement with a linear theory analysis performed on a restricted range of scales. From a tomographic analysis of the four LRG photometric redshift bins we find that the rate of structure growth is consistent with ΛCDM with an overall amplitude that is ≃ 5-7% lower than predicted by primary CMB measurements with modest (∼ 2σ) statistical significance. From the combined analysis of all four bins and their cross-correlations with Planck we obtain S 8 = 0.765 ± 0.023, which is less discrepant with primary CMB measurements than previous DESI LRG cross Planck CMB lensing results. From the cross-correlation with ACT we obtain S 8 = 0.790 +0.024 -0.027 , while when jointly analyzing Planck and ACT we find S 8 = 0.775 +0.019 -0.022 from our data alone and σ 8 = 0.772 +0.020 -0.023 with the addition of BAO data. These constraints are consistent with the latest Planck primary CMB analyses at the ≃ 1.6-2.2σ level, and are in excellent agreement with galaxy lensing surveys.

cosmological parameters from LSS↗

DOE OSTI2024

Deprotonated sulfamic acid and its homodimers: Does sulfamic acid adopt zwitterion during cluster growth?

Here we present a joint experimental and computational study on the geometric and electronic structures of deprotonated sulfamic acid (SA) clusters [(SA) n –H] – (n = 1, 2) employing negative ion photoelectron spectroscopy and high-level ab initio calculations. The photoelectron spectra provide the vertical/adiabatic detachment energy (VDE/ADE) of the sulfamate anion (SM – ) H 2 N•SO 3 – at 4.85 ± 0.05 and 4.58 ± 0.08 eV, respectively, and the VDE and ADE of the SM – •SA dimer at 6.41 ± 0.05 and 5.87 ± 0.08 eV, respectively. The significantly increased electron binding energies of the dimer confirm the enhanced electronic stability upon the addition of one SA molecule. The CCSD(T)-predicted VDEs/ADEs agree excellently with the experimental data, confirming the identified structures as the most stable ones. Two types of dimer isomers possessing different hydrogen bonding (HB) motifs are identified, corresponding to SM – binding to a zwitterionic SA (SM – •SA z ) and a canonical SA (SM – •SA c ), respectively. Two N–H$\cdots$O HBs and one superior O–H$\cdots$O HB are formed in the lowest-lying SM – •SA c , while SM – •SA z has three moderate N–H$\cdots$O HBs, with the former being 4.71 kcal/mol more stable. Further theoretical analyses reveal that the binding strength advantage of SM – •SA c over SM – •SA z arises from its significant contributions of orbital interactions between fragments, illustrating that sulfamate strongly interacts with its parent SA acid and preferably chooses the canonical SA in the subsequent cluster formations. Given the prominent presence of SA, this study provides the first evidence that the canonical dimer model of sulfamic acid should exist as a superior configuration during cluster growth.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2021

Fiber optic system for direct detection of CO 2 leakage in carbon storage wells (Abbreviated Final Report)

The feasibility study focused on the development of new fiber for distributed chemical sensing that will allow direct detection of CO2 leakages in the environment. This is particularly important for monitoring well integrity for carbon capture and storage (CSS), which can provide early warning for an incoming well failure and potential CO2 leaking through it. We proposed Raman or IR interrogation within gas-filled Holey Fibers (HoFs) interleaved with Fiber Bragg Grating (FBG) sections, so that the location and concentration of the gases would be provided simultaneously. The methodology would overcome current roadblocks to using fiber optics for CO2 (and other gases) detection in wells with direct in-situ measurements of concentration along with other important parameters such as temperature and pressure. We were able to assess commercially available IR/Raman hollow core fiber and demonstrated detection of CO2 through them in our controlled environment setups at various pressure conditions. We have also established the ability of drilling precisely with fs-lases side holes to enable penetration of CO2 into the hollow core fiber and reduce diffusion rates. Open joint collars were also explored with double functionality: to obtain splice to solid core fiber critical for field deployment and create gas ingress locations. Both diffusion-only and pressurized fiber system have been constructed following COMSOL based semi-hybrid optical /fluidodynamics models. FBGs have been identified and procured and characterized. Along the work we leveraged internal modeling/design, photonics/laser characterization, optical fiber fabrication, and AM lab capabilities to design, develop and test in-house components or assemblies. Our results indicate the potential of HoF for CO2 downhole direct detection.

25 ENERGY STORAGE↗

DOE OSTI2024

Chloride and Hydride Transfer as Keys to Catalytic Upcycling of Polyethylene into Liquid Alkanes

Abstract Transforming polyolefin waste into liquid alkanes through tandem cracking‐alkylation reactions catalyzed by Lewis‐acid chlorides offers an efficient route for single‐step plastic upcycling. Lewis acids in dichloromethane establish a polar environment that stabilizes carbenium ion intermediates and catalyzes hydride transfer, enabling breaking of polyethylene C−C bonds and forming C−C bonds in alkylation. Here, we show that efficient and selective deconstruction of low‐density polyethylene (LDPE) to liquid alkanes is achieved with anhydrous aluminum chloride (AlCl 3 ) and gallium chloride (GaCl 3 ). Already at 60 °C, complete LDPE conversion was achieved, while maintaining the selectivity for gasoline‐range liquid alkanes over 70 %. AlCl 3 showed an exceptional conversion rate of 5000 , surpassing other Lewis acid catalysts by two orders of magnitude. Through kinetic and mechanistic studies, we show that the rates of LDPE conversion do not correlate directly with the intrinsic strength of the Lewis acids or steric constraints that may limit the polymer to access the Lewis acid sites. Instead, the rates for the tandem processes of cracking and alkylation are primarily governed by the rates of initiation of carbenium ions and the subsequent intermolecular hydride transfer. Both jointly control the relative rates of cracking and alkylation, thereby determining the overall conversion and selectivity.

Zhang, Wei↗

DOE OSTI2024

Chloride and Hydride Transfer as Keys to Catalytic Upcycling of Polyethylene into Liquid Alkanes

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2022

A Constraint on Primordial B-modes from the First Flight of the Spider Balloon-borne Telescope

We present the first linear polarization measurements from the 2015 long-duration balloon flight of Spider, which is an experiment that is designed to map the polarization of the cosmic microwave background (CMB) on degree angular scales. The results from these measurements include maps and angular power spectra from observations of 4.8% of the sky at 95 and 150 GHz, along with the results of internal consistency tests on these data. While the polarized CMB anisotropy from primordial density perturbations is the dominant signal in this region of sky, Galactic dust emission is also detected with high significance. Galactic synchrotron emission is found to be negligible in the Spider bands. We employ two independent foreground-removal techniques to explore the sensitivity of the cosmological result to the assumptions made by each. The primary method uses a dust template derived from Planck data to subtract the Galactic dust signal. A second approach, which constitutes a joint analysis of Spider and Planck data in the harmonic domain, assumes a modified-blackbody model for the spectral energy distribution of the dust with no constraint on its spatial morphology. Using a likelihood that jointly samples the template amplitude and r parameter space, we derive 95% upper limits on the primordial tensor-to-scalar ratio from Feldman–Cousins and Bayesian constructions, finding r < 0.11 and r < 0.19, respectively. Roughly half the uncertainty in r derives from noise associated with the template subtraction. New data at 280 GHz from Spider's second flight will complement the Planck polarization maps, providing powerful measurements of the polarized Galactic dust emission.

79 ASTRONOMY AND ASTROPHYSICS↗