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NASA NTRS2022

Effects of Increasing the Category Resolution of the Sea Ice Thickness Distribution in a Coupled Climate Model on Arctic and Antarctic Sea Ice Mean State

Many modern sea ice models used in global climate models represent the subgrid-scale heterogeneity in sea ice thickness with an ice thickness distribution (ITD), which improves model realism by representing the significant impact of the high spatial heterogeneity of sea ice thickness on thermodynamic and dynamic processes. Most models default to five thickness categories. However, little has been done to explore the effects of the resolution of this distribution (number of categories) on sea-ice feedbacks in a coupled model framework and resulting representation of the sea ice mean state. Here, we explore this using sensitivity experiments in CESM2 with the standard 5 ice thickness categories and 15 ice thickness categories. Increasing the resolution of the ITD in a run with preindustrial climate forcing results in substantially thicker Arctic sea ice year-round. Analyses show that this is a result of the ITD influence on ice strength. With 15 ITD categories, weaker ice occurs for the same average thickness, resulting in a higher fraction of ridged sea ice. In contrast, the higher resolution of thin ice categories results in enhanced heat conduction and bottom growth and leads to only somewhat increased winter Antarctic sea ice volume. The spatial resolution of the ICESat-2 satellite mission provides a new opportunity to compare model outputs with observations of seasonal evolution of the ITD in the Arctic (ICESat-2; 2018–2021). Comparisons highlight significant differences from the ITD modeled with both runs over this period, likely pointing to underlying issues contributing to the representation of average thickness.

Madison M. Smith↗

DOE OSTI2019

Comprehensive End-To-End Design of Novel High Energy Density Materials: III. Fused Heterocyclic Energetic Compounds

In contrast to synthesis and experimental characterization that are usually expensive and time-consuming, a coupled combination of ab initio and group additive theoretical methods represents a powerful alternative to computationally design and characterize new materials with targeted properties. Heterocyclic energetic materials are considered attractive candidates to replace conventional high explosives, such as PETN, RDX, HMX, and TNT. Heterocycles enable an intriguing opportunity for combinatorial design of new classes of energetic materials with targeted performance and sensitivity properties and offer ways for an accurate analysis of structure–property correlations of the materials. By using a computational strategy that links methods of quantum chemistry and semiempirical statistical analysis, we designed, modeled, and characterized a series of novel linear and fused explosive compounds. Proposed materials with best combinations of performance and sensitivity parameters can be now considered as potential candidates for synthesis and experimental characterization.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2017

Extraction of geometrical structure of ethylene molecules by laser-induced electron diffraction combined with ab initio scattering calculations

In this paper, we measured angle-resolved high-energy electron spectra emitted from ${\mathrm{C}}_{2}{\mathrm{H}}_{4}$ in an intense laser field, extracted field-free electron-ion elastic scattering differential cross sections (DCSs) according to quantitative rescattering theory, and obtained molecular contrast factors (MCFs) subtracting the incoherent sum of DCSs of all the atoms in the molecule. Comparing the results with ab initio scattering calculations and employing least-squares fitting, we have extracted the C-C and C-H bond lengths of the molecule with ${\sim}5$ % uncertainty. Finally, this approach opens the way to retrieve the structure of hydrocarbon molecules, potentially at high temporal resolution, employing low collision energies where electron scattering is sensitive to the hydrogen atoms; and where the independent atom model calculations may fail to reproduce the experimentally extracted MCF.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2019

Monolingual but not bilingual infants demonstrate racial bias in social cue use

Abstract Bilingualism exerts early and pervasive effects on cognition, observable in infancy. Thus far, investigations of infant bilingual cognition have focused on sensitivity to visual memory, executive function, and linguistic sensitivity. Much less research has focused on how bilingualism impacts processing of social cues. The present study sought to investigate whether bilingualism modulates the expression of one aspect of social processing: early racial bias. Using a gaze‐following paradigm, we investigated whether 18‐ to 20‐month‐old monolingual and bilingual infants favored their own race. Results demonstrated that monolingual infants favored their own race in following a model whose direction of gaze signaled an event. In contrast, bilingual infants demonstrated race‐neutral gaze‐following patterns, relying more heavily on the reliability of the behavior of the model over race. Findings suggest that bilingualism may have protective effects against the early emergence of racial bias.

Singh, Leher↗

DOE OSTI2014

TH-A-18C-10: Dynamic Intensity Weighted Region of Interest Imaging

Purpose: For image guidance tasks full image quality is not required throughout the entire image. With dynamic filtration of the kV imaging beam the noise properties of the CT image can be locally controlled, providing a high quality image around the target volume with a lower quality surrounding region while providing substantial dose sparing to the patient as well as reduced scatter fluence on the detector. Methods: A dynamic collimation device with 3mm copper blades has been designed to mount in place of the bowtie filter on the On-Board Imager (Varian Medical Systems). The beam intensity is reduced by 95% behind the copper filters and the aperture is controlled dynamically to conformally illuminate a given ROI during a standard cone-beam CT scan. A data correction framework to account for the physical effects of the collimator prior to reconstruction was developed. Furthermore, to determine the dose savings and scatter reduction a monte carlo model was built in BEAMnrc with specifics from the Varian Monte Carlo Data Package. The MC model was validated with Gafchromic film. Results: The reconstructed image shows image quality comparable to a standard scan in the specified ROI, with higher noise and streaks in the outer region but still sufficient information for alignment to high contrast structures. The monte carlo modeling showed that the scatter-to-primary ratio was reduced from 1.26 for an unfiltered scan to 0.45 for an intensity weighted scan, suggesting that image quality may be improved in the inner ROI. Dose in the inner region was reduced 10–15% due to reduced scatter and by as much as 75% in the outer region. Conclusion: Dynamic intensity-weighted ROI imaging allows reduction of imaging dose to sensitive organs away from the target region while providing images that retain their utility for patient setup and procedure guidance. Funding was provided in part by Varian Medical Systems and NIH Grants 1RO1CA120540, T32EB002103, S10 RR021039 and P30 CA14599. The contents of this work are solely the responsibility of the authors and do not necessarily represent the official views of any of the supporting organizations.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

DOE OSTI2014

Development of an aerosol microphysical module: Aerosol Two-dimensional bin module for foRmation and Aging Simulation (ATRAS)

Number concentrations, size distributions, and mixing states of aerosols are essential parameters for accurate estimation of aerosol direct and indirect effects. In this study, we developed an aerosol module, designated Aerosol Two-dimensional bin module for foRmation and Aging Simulation (ATRAS), that can represent these parameters explicitly by considering new particle formation (NPF), black carbon (BC) aging, and secondary organic aerosol (SOA) processes. A two-dimensional bin representation is used for particles with dry diameters from 40 nm to 10 µm to resolve both aerosol size (12 bins) and BC mixing state (10 bins) for a total of 120 bins. The particles with diameters from 1 to 40 nm are resolved using an additional 8 size bins to calculate NPF. The ATRAS module was implemented in the WRF-chem model and applied to examine the sensitivity of simulated mass, number, size distributions, and optical and radiative parameters of aerosols to NPF, BC aging and SOA processes over East Asia during the spring of 2009. BC absorption enhancement by coating materials was about 50% over East Asia during the spring, and the contribution of SOA processes to the absorption enhancement was estimated to be 10 – 20% over northern East Asia and 20 – 35% over southern East Asia. A clear north-south contrast was also found between the impacts of NPF and SOA processes on cloud condensation nuclei (CCN) concentrations: NPF increased CCN concentrations at higher supersaturations (smaller particles) over northern East Asia, whereas SOA increased CCN concentrations at lower supersaturations (larger particles) over southern East Asia. Application of ATRAS to East Asia also showed that the impact of each process on each optical and radiative parameter depended strongly on the process and the parameter in question. The module can be used in the future as a benchmark model to evaluate the accuracy of simpler aerosol models and examine interactions between NPF, BC aging, and SOA processes under different meteorological conditions and emissions.

Matsui, H.↗

NASA NTRS2018

Weak Hydrological Sensitivity to Temperature Change over Land, Independent of Climate Forcing

We present the global and regional hydrological sensitivity (HS) to surface temperature changes, for perturbations to CO2, CH4, sulfate and black carbon concentrations, and solar irradiance. Based on results from ten climate models, we show how modeled global mean precipitation increases by 2-3% per kelvin of global mean surface warming, independent of driver, when the effects of rapid adjustments are removed. Previously reported differences in response between drivers are therefore mainly ascribable to rapid atmospheric adjustment processes. All models show a sharp contrast in behavior over land and over ocean, with a strong surface temperature-driven (slow) ocean HS of 3-5%/K, while the slow land HS is only 0-2%/K. Separating the response into convective and large-scale cloud processes, we find larger inter-model differences, in particular over land regions. Large-scale precipitation changes are most relevant at high latitudes, while the equatorial HS is dominated by convective precipitation changes. Black carbon stands out as the driver with the largest inter-model slow HS variability, and also the strongest contrast between a weak land and strong sea response. We identify a particular need for model investigations and observational constraints on convective precipitation in the Arctic, and large-scale precipitation around the Equator.

Samset, B. H.↗

NASA NTRS2022

Direct Imaging and Spectroscopy of Exoplanetary Systems with the JWST Early Release Science Program

The direct characterization of exoplanetary systems with high contrast imaging is among the highest priorities for the broader exoplanet community. As large space missions will be necessary for detecting and characterizing exo-Earth twins, developing the techniques and technology for direct imaging of exoplanets is a driving focus for the community. For the first time, JWST will directly observe extrasolar planets at mid-infrared wavelengths beyond 5 μm, deliver detailed spectroscopy revealing much more precise chemical abundances and atmospheric conditions, and provide sensitivity to analogs of our solar system ice-giant planets at wide orbital separations, an entirely new class of exoplanet. However, in order to maximise the scientific output over the lifetime of the mission, an exquisite understanding of the instrumental performance of JWST is needed as early in the mission as possible. In this paper, we describe our 55-hour Early Release Science Program that will utilize all four JWST instruments to extend the characterisation of planetary mass companions to ∼15-20 μm as well as image a circumstellar disk in the mid-infrared with unprecedented sensitivity. Our program will also assess the performance of the observatory in the key modes expected to be commonly used for exoplanet direct imaging and spectroscopy, optimize data calibration and processing, and generate representative datasets that will enable a broad user base to effectively plan for general observing programs in future cycles.

Michael W McElwain↗

NASA NTRSDate not supplied

Exploring Radiation, Water and Energy Closure in Key Deep Tropical Regions Over the Last 3 Decades

The closure of global energy and water budgets at various time scales depends heavily upon the on the processes of water and energy exchange in the deep tropics. A key process observed is the change in convection regimes from disorganized convection to organized deep convection. During these periods an imbalance in key tropical regions is observed of water budget terms between observations and atmospheric reanalysis systems, implying that processes are not simulated well. For instance, periods of imbalance in the water budget may be at least partly attributed to precipitation estimates due to the transition between cloud and precipitation systems in which ice cloud affects microwave radar estimates (Lietmann-Niimi et al. 2024, submitted). A recent paper by Hsaio et al (2023, pre-published version) found that the transition process is characterized by wind shear and longwave cloud radiative feedback signatures as well. This is just one example how these processes also affect the radiative fluxes and thus the energy budget at the TOA. In this presentation, we assess the net radiative budget and components in the deep tropics by comparing multiple data products (GEWEX SRB Rel4IP, CERES EBAF/SYN1deg Ed4.2, ISSCP FH, etc.) and describing the temporal variability of energy balance terms across the deep tropics for the period from 1988 to near present in six key oceanic regions. These six key tropical oceanic regions are West Indian Ocean, the south Indian Ocean east, tropical western, central and eastern Pacific Ocean, and Tropical Atlantic Ocean. In these regions we assess the sensitivity of the fluxes as a function of fluctuations in cloud types in response to various larger scale atmospheric processes (e.g. El Niño, Indian Ocean Dipole). We assess this variability of the radiative flux anomalies (including the net TOA, surface and the atmospheric divergence fluxes) against water vapor divergence, cloud properties (include ISCCP “Weather States, Tselioudis et al. 2021) and larger scale wind shear to assess the uncertainties of energy closure in these regions. These are contrasted against the modeled radiative fluxes from ERA-5 and MERRA-2. Ocean buoy measurements of radiative fluxes are utilized to help assess data radiative flux uncertainty over the nearly 40 year period. In general, the variability for overlap periods of these various data products agrees well, but there are significant differences in the net fluxes that vary according to the rendering of surface, atmospheric, aerosol and cloud properties. These differences also affect closure terms and inferences on systematic uncertainties within the observational estimates. We conclude with recommendations for continuing work

Radiation budget↗

DOE OSTI2018

Cadmium(II) complexes with monoiodo- and dibromodipyrromethenes: synthesis, molecular structure, spectral-luminescent properties, and stability in solutions

Cadmium(II) chelates with 4-iodo-, 5,5´-, and 4,4´-dibromo-2,2´-dipyrromethenes (HL{sup 1}, HL{sup 2}, and HL{sup 3}, respectively) with the composition of [CdL{sub 2}] were synthesized. The influence of structural features of their molecules and properties of the medium on the characteristics of absorption and fluorescence spectra, and also on the thermodynamic stability constants in solutions was evaluated. The results of quantum chemical calculations revealed that the additional coordination interactions between the bromine atoms at the α-positions of dipyrromethene ligands and the complexing atom are possible in the molecular structure of α,α´- dibromosubstituted dipyrromethenate [Cd(L{sup 2}){sub 2}] in contrast with β-halogenated analogues [Cd(L{sup 1}){sub 2}] and [Cd(L{sup 3}){sub 2}].

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2024

Robust finite-temperature many-body scarring on a quantum computer

Mechanisms for suppressing thermalization in disorder-free many-body systems, such as Hilbert space fragmentation and quantum many-body scars, have recently attracted much interest in foundations of quantum statistical physics and potential quantum information processing applications. However, their sensitivity to realistic effects such as finite temperature remains largely unexplored. Here, we have utilized IBM's Kolkata quantum processor to demonstrate an unexpected robustness of quantum many-body scars at finite temperatures when the system is prepared in a thermal Gibbs ensemble. We identify such robustness in the PXP model, which describes quantum many-body scars in experimental systems of Rydberg atom arrays and ultracold atoms in tilted Bose-Hubbard optical lattices. By contrast, other theoretical models which host exact quantum many-body scars are found to lack such robustness and their scarring properties quickly decay with temperature. Our study sheds light on the important differences between scarred models in terms of their algebraic structures, which impacts their resilience to finite temperature. Published by the American Physical Society 2024

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

DOE OSTI2021

AlSb as a material for high index contrast nanophotonics

High contrast materials, i.e., materials with a high refractive index and low optical loss, are of wide interest for nanophotonics and metasurface designs at optical and near infrared wavelengths. We explore aluminum antimonide (AlSb) as a high contrast nanophotonic material, using the design of high contrast gratings (HCGs) for low loss dielectric mirrors as an example. The high index of refraction and low absorption coefficient of AlSb in the visible wavelength range enable designs of HCGs that can be effectively optimized to form mirrors with 93.5% reflectivity at red visible wavelengths. We detail a co-sputtering synthesis method for AlSb films, and achieve our target high index of refraction of 3.5 for 635 nm light. We also find that the high sensitivity of AlSb oxidation requires specific handling procedures in developing deposition processes to yield a near zero absorption coefficient.

Bauser, Haley C.↗

NASA NTRS1996

Ocean observations with EOS/MODIS: Algorithm development and post launch studies

An investigation of the influence of stratospheric aerosol on the performance of the atmospheric correction algorithm is nearly complete. The results indicate how the performance of the algorithm is degraded if the stratospheric aerosol is ignored. Use of the MODIS 1380 nm band to effect a correction for stratospheric aerosols was also studied. Simple algorithms such as subtracting the reflectance at 1380 nm from the visible and near infrared bands can significantly reduce the error; however, only if the diffuse transmittance of the aerosol layer is taken into account. The atmospheric correction code has been modified for use with absorbing aerosols. Tests of the code showed that, in contrast to non absorbing aerosols, the retrievals were strongly influenced by the vertical structure of the aerosol, even when the candidate aerosol set was restricted to a set appropriate to the absorbing aerosol. This will further complicate the problem of atmospheric correction in an atmosphere with strongly absorbing aerosols. Our whitecap radiometer system and solar aureole camera were both tested at sea and performed well. Investigation of a technique to remove the effects of residual instrument polarization sensitivity were initiated and applied to an instrument possessing (approx.) 3-4 times the polarization sensitivity expected for MODIS. Preliminary results suggest that for such an instrument, elimination of the polarization effect is possible at the required level of accuracy by estimating the polarization of the top-of-atmosphere radiance to be that expected for a pure Rayleigh scattering atmosphere. This may be of significance for design of a follow-on MODIS instrument. W.M. Balch participated on two month-long cruises to the Arabian sea, measuring coccolithophore abundance, production, and optical properties. A thorough understanding of the relationship between calcite abundance and light scatter, in situ, will provide the basis for a generic suspended calcite algorithm.

Gordon, Howard R.↗

NASA NTRS1997

1,25 (OH)2D3 enhances PTH-induced Ca2+ transients in preosteoblasts by activating L-type Ca2+ channels

We previously demonstrated electrophysiologically that 1,25-dihydroxyvitamin D3 [1,25(OH)2D3] shifts the activation threshold of L-type Ca2+ channels in osteoblasts toward the resting potential and prolongs mean open time. Presently, we used single-cell Ca2+ imaging to study the combined effects of 1,25(OH)2D3 and parathyroid hormone (PTH) during generation of Ca2+ transients in fura 2-loaded MC3T3-E1 cells. Pretreatment with 1,25(OH)2D3 concentrations, which alone did not produce Ca2+ transients, consistently enhanced Ca2+ responses to PTH. Enhancement was dose dependent over the range of 1 to 10 nM and was blocked by pretreatment with 5 microM nitrendipine during pretreatment. A 1,25(OH)2D3 analog that activates L-type channels and shifts their activation threshold also enhanced PTH responses. In contrast, an analog devoid of membrane Ca2+ effects did not enhance PTH-induced Ca2+ transients. The PTH-induced Ca2+ transient involved activation of a dihydropyridine-insensitive cation channel that was inhibited by Gd3+. Together, these data suggest that 1,25(OH)2D3 increases osteoblast responsiveness to PTH through rapid modification of L-type Ca2+ channel gating properties, whose activation enhances Ca2+ entry through other channels such as the PTH-responsive, Gd(3+)-sensitive cation channel.

Non-NASA Center↗

DOE OSTI2023

From Layered Antiferromagnet to 3D Ferromagnet: LiMnBi-to-MnBi Magneto-Structural Transformation

Here, the intermetallic compound LiMnBi was synthesized by the two-step solid-state reaction from the elements. The synthesis temperature of 850 K was selected based on in-situ high-temperature powder X-ray diffraction data. LiMnBi crystalizes in the layered-like PbClF structure type (a = 4.3131(7) Å, c = 7.096(1) Å at 100 K, P4/nmm space group, Z = 2). LiMnBi structure is built of the alternating [MnBi] and Li layers, as determined from single-crystal X-ray diffraction data. Magnetic properties measurements and solid-state 7 Li Nuclear Magnetic Resonance data collected for polycrystalline LiMnBi samples indicate the long-range antiferromagnetic ordering of Mn sublattice at ~340 K, with no superconductivity down to 5 K detected. LiMnBi is air- and water-sensitive. In aerobic conditions, Li can be extracted from LiMnBi structure to form Li 2 O/LiOH and MnBi (NiAs structure type, P6 3 /mmc). The obtained MnBi polymorph was previously reported to be one of the strongest rare-earth-free ferromagnets, yet its bulk synthesis in powder form is cumbersome. The proposed magneto-structural transformation from ternary LiMnBi to ferromagnetic MnBi involves condensation of the MnBi4 tetrahedra upon Li deintercalation and is exclusive to LiMnBi. In contrast, ferromagnetic MnBi cannot be obtained from either isostructural NaMnBi and KMnBi, or from the structurally related CaMn 2 Bi 2 . Such a distinctive transformation in the case of LiMnBi is presumed to be due to its fitting reactivity to yield MnBi and favorable interlayer distance between [MnBi] layers, while the interlayer distance in NaMnBi and KMnBi structural analogs is unfavorably long. The studies of delithiation from the layered-like LiMnBi under different chemical environments indicate that the yield of the MnBi depends on the type of solvent used and the kinetics of the reaction. A slow rate and mild reaction media lead to a high fraction of the MnBi product. The saturation magnetization of the “as-prepared” MnBi is ~50 % of the expected value of 81.3 emu/g. Overall, this study adds a missing member to the family of ternary pnictides and illustrates how soft-chemistry methods can be used to obtain “difficult-to-synthesize” compounds.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2023

Deconvoluting Structures of Component Plant Biopolymers Using Deuterium Labeled Brassica oleracea Stems

Several Brassica species are cultivated globally for the production of seed oils as food, lubricants, and increasingly biofuels. The stem and leaf residues of these herbaceous dicotyledonous crops constitute another feedstock for biofuels and other products. Plant cell walls are complex, multipolymeric structures that consist primarily of polysaccharides and lignin. Cellulose chains coalesce to form crystalline microfibrils while the amorphous biopolymers, hemicellulose, and lignin form a network structure and fill the interstitial space. Neutron scattering has been used for the structural study of the assembly and deconstruction of the plant cell walls. However, similar neutron sensitivity of the different amorphous biopolymers has made structural association to individual component biopolymers nontrivial and ambiguous. To improve the association of structural features to specific biopolymer components, partial deuteration of the plant cell wall can be employed to increase the difference in the neutron scattering length density between amorphous carbohydrate and lignin plant polymers. Vegetative stems from partially deuterated Brassica oleracea acephala (kale) plants were obtained commercially, and the plant cell wall structures were studied by contrast-variation small-angle neutron scattering (CV-SANS) and Fourier-transform infrared spectroscopy (FTIR). FTIR results indicated that deuterium substitution for hydrogen in the carbohydrates was higher than that in lignin. By combining CV-SANS and FTIR results, the neutron scattering length density (nSLD) of the polysaccharides and lignin was determined to match nSLD of 65%:35% and 48%:52% D 2 O/H 2 O solvent mixtures, respectively. These nSLD values were higher than the nSLD values of polysaccharides and lignin for H 2 O grown biopolymers. The nSLD increase correlates to replacing about 42.5% of hydrogens present as both C–H and O–H groups in cellulose with deuterium atoms, while only 21% for lignin. In conclusion, this study lays the foundation to use partially deuterated plants to deconvolute structural features of the different component biopolymers, especially cellulose, hemicellulose, and lignin, of the plant cell wall without introducing unintended structural modifications due to the pretreatment extraction processes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2021

Long-term warming in a Mediterranean-type grassland affects soil bacterial functional potential but not bacterial taxonomic composition

Abstract Climate warming is known to impact ecosystem composition and functioning. However, it remains largely unclear how soil microbial communities respond to long-term, moderate warming. In this study, we used Illumina sequencing and microarrays (GeoChip 5.0) to analyze taxonomic and functional gene compositions of the soil microbial community after 14 years of warming (at 0.8–1.0 °C for 10 years and then 1.5–2.0 °C for 4 years) in a Californian grassland. Long-term warming had no detectable effect on the taxonomic composition of soil bacterial community, nor on any plant or abiotic soil variables. In contrast, functional gene compositions differed between warming and control for bacterial, archaeal, and fungal communities. Functional genes associated with labile carbon (C) degradation increased in relative abundance in the warming treatment, whereas those associated with recalcitrant C degradation decreased. A number of functional genes associated with nitrogen (N) cycling (e.g., denitrifying genes encoding nitrate-, nitrite-, and nitrous oxidereductases) decreased, whereas nifH gene encoding nitrogenase increased in the warming treatment. These results suggest that microbial functional potentials are more sensitive to long-term moderate warming than the taxonomic composition of microbial community.

59 BASIC BIOLOGICAL SCIENCES↗

DOE OSTI2019

Structural and Reorientational Dynamics of Tetrahydroborate (BH4-) and Tetrahydrofuran (THF) in a Mg(BH4)2 3THF Adduct: Neutron-Scattering Characterization

Metal borohydrides are considered promising materials for hydrogen storage applications due to their high volumetric and gravimetric hydrogen density. Recently, different Lewis bases have been complexed with Mg(BH4)2 in efforts to improve hydrogenation/dehydrogenation properties. Notably, Mg(BH4)2 xTHF adducts involving tetrahydrofuran (THF; C4H8O) have proven to be especially interesting. This work focuses on exploring the physicochemical properties of the THF-rich Mg(BH4)2 3THF adduct using neutron-scattering methods and molecular DFT calculations. Structural analysis, based on neutron diffraction measurements of Mg(11BH4)2 3TDF (D-deuterium), has confirmed a lowering of the symmetry upon cooling, from monoclinic C2/c to P[1 with combining macron] via a triclinic distortion. Vibrational properties are strongly influenced by the THF environment, showing a splitting in spectral features as a result of changes in the bond lengths, force constants, and lowering of the overall symmetry. Interestingly, the orientational mobilities of the BH4- anions obtained from quasielastic neutron scattering (QENS) are not particularly sensitive to the presence of THF and compare well with the mobilities of BH4- anions in unsolvated Mg(BH4)2. The QENS data point to uniaxial 180 degree jump reorientations of the BH4- anions around a preferred C2 anion symmetry axis. The THF rings are also found to be orientationally mobile, undergoing 180 degree reorientational jumps around their C2 molecular symmetry axis with jump frequencies about an order of magnitude lower than those for the BH4- anions. In contrast, no dynamical behavior of the THF rings is observed with QENS for a more THF-deficient 2Mg(BH4)2 THF adduct. This lack of comparable THF mobility may reflect a stronger Mg2+-THF bonding interaction for lower THF/Mg(BH4)2 stoichiometric ratios, which is consistent with DFT calculations showing a decrease in the binding energy with each additional THF ring in the adduct. Based on the combined experimental and computational results, we propose that combining THF and Mg(BH4)2 is beneficial to (i) preventing weakly bound THF from coming free from the Mg2+ cation and reducing the concentration of any unwanted impurity in the hydrogen and (ii) disrupting the stability of the crystalline phase, leading to a lower melting point and enhanced kinetics for any potential hydrogen storage applications.

36 MATERIALS SCIENCE↗