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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 145 records · Page 8

Engineering Thermal Transport across Layered Graphene–MoS 2 Superlattices

Layering two-dimensional van der Waals materials provides a high degree of control over atomic placement, which could enable tailoring of vibrational spectra and heat flow at the sub-nanometer scale. In this work, using spatially resolved ultrafast thermoreflectance and spectroscopy, we uncover the design rules governing cross-plane heat transport in superlattices assembled from monolayers of graphene (G) and MoS 2 (M). Using a combinatorial experimental approach, we probe nine different stacking sequences, G, GG, MG, GGG, GMG, GGMG, GMGG, GMMG, and GMGMG, and identify the effects of vibrational mismatch, interlayer adhesion, and junction asymmetry on thermal transport. Pure G sequences display evidence of quasi-ballistic transport, whereas adding even a single M layer strongly disrupts heat conduction. The experimental data are described well by molecular dynamics simulations, which include thermal expansion, accounting for the effect of finite temperature on the interlayer spacing. The simulations show that an increase of ~2.4% in the layer separation of GMGMG, relative to its value at 300 K, can lead to a doubling of the thermal resistance. Using these design rules, we experimentally demonstrate a five-layer GMGMG superlattice “thermal metamaterial” with an ultralow effective cross-plane thermal conductivity comparable to that of air.

2D materials↗

Reducing sputter induced stress and damage for efficient perovskite/silicon tandem solar cells

Reducing damages caused by sputtering of transparent conductive oxide (TCO) electrodes is critical in achieving highly efficient and stable perovskite/silicon tandem solar cells. Here we study the sputter caused damage to bathocuproine (BCP), which is widely used in highly efficient p-i-n structure single junction perovskite solar cells. While BCP buffer layer protects the underneath layers from damage, itself can be damaged by sputtering of TCOs at a wide range of target-substrate distances, supported by molecular dynamic simulation. More intriguingly, it is observed that TCO easily peeled off after sputtering when the sputtering target is close to substrate. This is ascribed to formation of stress during cooling down process after sputtering due to different thermal expansion coefficients of the layers. Our studies explain why tin oxide (SnO2) made by atomic layer deposition can replace BCP for a much better tandem device performance. SnO2 has high affinity with sputtered TCO electrode to suppress peeling-off issue and has higher bond energy to resist sputter induced damage, thus it allows a wider window of target-substrate distances than BCP during TCO sputtering. Ultimately, we demonstrate an efficient perovskite/silicon monolithic tandem solar cell with efficiency of 26.0% to illustrate the beneficial effects of reduced stress and damage.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Bridging the length scales in ionic separations via data-driving machine learning

We pursued a data science driven machine learning (ML) approach that blended molecular scale attributes informed from molecular dynamics (MD) simulation and materials properties to the selectivity and energy efficiency in targeted ionic separations using electric fields. The model mixtures investigated for ionic separations are pH sensitive and include organic acids, silica and boron, transition metals, such as copper and chromium. There were two major research thrusts of this project. Firstly, we investigated surrogate models and deep learning that relate material chemistries and structures to selective transport of ionic species under applied electric fields. Secondly we investigated how the bipolar junction interfacial design and water dissociation catalyst in bipolar membranes affect reverse bias polarization behavior and pH modulation in deionization platforms as a function of the platform operating parameters (e.g., cell voltage, residence time, and salt feed concentration). As a result of this work, we also were able to start a new direction, namely ML models for molecular design of surfactants.

36 MATERIALS SCIENCE↗

Navier: Dataflow Architecture for Computation Chemistry

Navier’s objectives were two evaluate the use of emerging technologies, especially dataflow accelerators, for high-performance computing (HPC) applications, specifically in the domain of chemistry, and to develop a prototype software stack to support such applications. Navier builds on capabilities previously developed by synergistic projects, such as PNNL Data Model Convergence (DMC) LDRD Hardware Advanced Workflows (HAW) and DuOMO, as well as DOE ARIAA. Throughout its 18 months, the Navier team developed new capabilities and artifacts at all levels of the HW/SW stack, provided a seamless way to integrate novel computing architectures (Sambanova SN10 and Xilinx Versal AI) into an existing software stack, developed chemistry workflows, data analytics tools, and HPC molecular dynamics workflows that leverage the developed stack and PNNL institutional investments in emerging architectures. Navier also explored the use of active learning to accelerate a computational chemistry workflow for organic molecules on PNNL Junction cluster (in collaboration with AMD/Xilinx). Navier developed tools, methodologies, and studies for hardware software co-design and (sparse) dataflow accelerators that are composable and can be used together or separately. These methodologies are now used in other projects, such as DOE AMAIS and HPDA. This report describes Navier’s achievement, the developed tools and methodologies, and the research findings and conclusions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Molecular architecture and functional dynamics of the pre-incision complex in nucleotide excision repair

Nucleotide excision repair (NER) is vital for genome integrity. Yet, our understanding of the complex NER protein machinery remains incomplete. Combining cryo-EM and XL-MS data with AlphaFold2 predictions, we build an integrative model of the NER pre-incision complex(PInC). Here TFIIH serves as a molecular ruler, defining the DNA bubble size and precisely positioning the XPG and XPF nucleases for incision. Using simulations and graph theoretical analyses, we unveil PInC’s assembly, global motions, and partitioning into dynamic communities. Remarkably, XPG caps XPD’s DNA-binding groove and bridges both junctions of the DNA bubble, suggesting a novel coordination mechanism of PInC’s dual incision. XPA rigging interlaces XPF/ERCC1 with RPA, XPD, XPB, and 5' ssDNA, exposing XPA’s crucial role in licensing the XPF/ERCC1 incision. Mapping disease mutations onto our models reveals clustering into distinct mechanistic classes, elucidating xeroderma pigmentosum and Cockayne syndrome disease etiology.

60 APPLIED LIFE SCIENCES↗

Crystal structure of Escherichia coli thiamine pyrophosphate-sensing riboswitch in the apo state

The thiamine pyrophosphate (TPP)-sensing riboswitch is one of the earliest discovered and most widespread riboswitches. Numerous structural studies have been reported for this riboswitch bound with various ligands. However, the ligand-free (apo) structure remains unknown. Here, we report a 3.1 Å resolution crystal structure of Escherichia coli TPP riboswitch in the apo state, which exhibits an extended, Y-shaped conformation further supported by small-angle X-ray scattering data and driven molecular dynamics simulations. The loss of ligand interactions results in helical uncoiling of P5 and disruption of the key tertiary interaction between the sensory domains. Opening of the aptamer propagates to the gene-regulatory P1 helix and generates the key conformational flexibility needed for the switching behavior. Much of the ligand-binding site at the three-way junction is unaltered, thereby maintaining a partially preformed pocket. Together, these results paint a dynamic picture of the ligand-induced conformational changes in TPP riboswitches that confer conditional gene regulation.

59 BASIC BIOLOGICAL SCIENCES↗

Visualizing the unusual spectral weight transfer in DyBa2Cu3O7–δ thin film

Abstract We report a Spectroscopic Imaging Scanning Tunneling Microscopy (SI-STM) study of a DyBa 2 Cu 3 O 7-δ (DBCO) thin film ( T c ~ 79 K) synthesized by the molecular beam epitaxy (MBE). We observed an unusual transfer of spectral weight in the local density of states (LDOS) spectra occurring only within the superconducting gap. By a systematic control of the tip-sample distance and the junction resistance, we demonstrate that the spectral weight transfer can be switched at a nano-meter length scale. These results suggest that an interaction between the STM tip and the sample alters the electronic configurations in the film. This probably originates from a combination of an intrinsic band bending at the interface between the surface and the bulk, and a tip-induced band bending. These results may open a new avenue for band engineering and applications of thin films of high- T c cuprates.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Magnetic molecules lose identity when connected to different combinations of magnetic metal electrodes in MTJ-based molecular spintronics devices (MTJMSD)

Abstract Understanding the magnetic molecules’ interaction with different combinations of metal electrodes is vital to advancing the molecular spintronics field. This paper describes experimental and theoretical understanding showing how paramagnetic single-molecule magnet (SMM) catalyzes long-range effects on metal electrodes and, in that process, loses its basic magnetic properties. For the first time, our Monte Carlo simulations, verified for consistency with regards to experimental studies, discuss the properties of the whole device and a generic paramagnetic molecule analog (GPMA) connected to the combinations of ferromagnet-ferromagnet, ferromagnet-paramagnet, and ferromagnet-antiferromagnet metal electrodes. We studied the magnetic moment vs. magnetic field of GPMA exchange coupled between two metal electrodes along the exposed side edge of cross junction-shaped magnetic tunnel junction (MTJ). We also studied GPMA-metal electrode interfaces’ magnetic moment vs. magnetic field response. We have also found that the MTJ dimension impacted the molecule response. This study suggests that SMM spin at the MTJ exposed sides offers a unique and high-yield method of connecting molecules to virtually endless magnetic and nonmagnetic electrodes and observing unprecedented phenomena in the molecular spintronics field.

42 ENGINEERING↗

All-perovskite tandem solar cells with improved grain surface passivation

All-perovskite tandem solar cells hold the promise of surpassing the efficiency limits of single-junction solar cells; however, until now, the best-performing all-perovskite tandem solar cells have exhibited lower certified efficiency than have single-junction perovskite solar cells. A thick mixed Pb–Sn narrow-bandgap subcell is needed to achieve high photocurrent density in tandem solar cells, yet this is challenging owing to the short carrier diffusion length within Pb–Sn perovskites. Here we develop ammonium-cation-passivated Pb–Sn perovskites with long diffusion lengths, enabling subcells that have an absorber thickness of approximately 1.2 μm. Molecular dynamics simulations indicate that widely used phenethylammonium cations are only partially adsorbed on the surface defective sites at perovskite crystallization temperatures. The passivator adsorption is predicted to be enhanced using 4-trifluoromethyl-phenylammonium (CF3-PA), which exhibits a stronger perovskite surface-passivator interaction than does phenethylammonium. By adding a small amount of CF3-PA into the precursor solution, we increase the carrier diffusion length within Pb–Sn perovskites twofold, to over 5 μm, and increase the efficiency of Pb–Sn perovskite solar cells to over 22%. Here, we report a certified efficiency of 26.4% in all-perovskite tandem solar cells, which exceeds that of the best-performing single-junction perovskite solar cells. Encapsulated tandem devices retain more than 90% of their initial performance after 600 h of operation at the maximum power point under 1 Sun illumination in ambient conditions.

14 SOLAR ENERGY↗

Topology-Informed Design Rules for Deconstructable Thermoset Copolymer Networks

Existing models of thermoset deconstruction facilitated by incorporating cleavable comonomers rely on a mean-field reverse gel point paradigm, which predicts network dissolution once cleavable bonds reach a critical stoichiometric threshold, but does not account for where those bonds reside within the network architecture. Using reactive coarse-grained molecular dynamics simulations coupled with graph-theoretic analysis, we extend this stoichiometric picture to show that deconstructability is governed by the curing-imprinted network topology rather than stoichiometry alone. This topological organization is hierarchical: at the local scale, the elastic effectiveness of cross-link junctions determines which cross-links constitute the load-bearing scaffold; at the mesoscale, the cross-linking rate kinetically templates that scaffold into topologically modular communities─densely cross-linked clusters connected by sparse bridging strands that sustain network connectivity. Using betweenness centrality to identify nodes that disproportionately lie on intercommunity shortest paths, we demonstrate that effective deconstruction of the network into macromolecular fragments requires cleavable comonomers to intercept these high-centrality bridging strands. We further find that under uniform, disassortative comonomer incorporation, this topological requirement provides a mechanistic basis for extending the reverse gel point to incorporate network topology. We also show that modularity imposes a fundamental limit on fragment uniformity that persists even when the centrality requirement is met. Finally, we demonstrate that chain stiffness provides a nearly independent lever to suppress mechanically redundant cross-links and raise the glass transition temperature without significantly altering the deconstruction outcome. Together, these findings reframe the thermoset design space around network topology and provide actionable guidelines for engineering thermoset copolymers with predictable deconstructability and targeted thermomechanical performance.

coarse-grained molecular dynamics↗

Tunable and Robust Optical and Structural Properties of a Cooperative Squaraine-Dye Aggregate-DNA DX-DAE Tile System

Molecular excitons, which are excitations delocalized over multiple dyes in a wavelike manner, are of interest for a wide range of applications, including quantum information science. Numerous studies have templated a variety of synthetic dyes via a DNA scaffold to induce dye aggregation to create molecular excitons upon photoexcitation. Dye aggregate optical properties are critically dependent on relative dye geometry and local environment; therefore, an understanding of dye-dye and DNA-dye interactions is critical for advancing toward more complex DNA-dye systems. The extensively studied DNA Holliday junction (HJ) and less-studied double-crossover (DX) tile motif are fundamental test beds for designing complex and ultimately modular DNA-dye architectures. Here, we report the first study of single-linked squaraine dye aggregation and exciton delocalization on a larger and more stable (compared with the HJ) DX tile motif. We first highlight a few DNA-dye constructs that support single dyes and aggregates with distinct optical properties that are both tunable—through sample design, buffer conditions, and heat treatment—and robust to environment changes, including transfer to solid phase. Next, we assess several experimental and design considerations that demonstrate directed dye-driven assembly of a novel double-tile DNA configuration. Our results demonstrate that single-linked squaraine dyes templated to DX tiles provide a viable research path to design and evaluate dye aggregate networks that support exciton delocalization. We include herein the first report of exciton delocalization in the solid phase in a DNA-dye construct. Additionally, our findings indicate that dye aggregation impacts the assembly of the DNA-dye construct, and, in some cases, thereby cooperates with the DNA to determine a final robust system configuration. Finally, we show that a controlled annealing schedule can be employed to promote the homogeneous assembly of DNA-dye constructs. The findings in this study contribute to the understanding of DNA-dye systems and the relevant factors involved in their directed assembly to achieve specific constructs with desirable properties.

36 MATERIALS SCIENCE↗

Insights into negative differential resistance in MoS 2 Esaki diodes: A first-principles perspective

MoS 2 is a two-dimensional material with a band gap depending on the number of layers and tunable by an external electric field. The experimentally observed intralayer band-to-band tunneling and interlayer band-to-band tunneling in this material present an opportunity for new electronic applications in tunnel field-effect transistors. However, such a widely accepted concept has yet to be been supported by theoretical investigations based on first principles. In this paper, using density functional theory, in conjunction with nonequilibrium Green's function techniques and our electric field gating method, enabled by a large-scale computational approach, we study the relation between band alignment and transmission in planar and side-stack MoS 2 p–i–n junction configurations. Here, we demonstrate the presence of negative differential resistance for both in-plane and interlayer current, a staple characteristic of tunnel diode junctions, and analyze the physical origin of such an effect. Electrostatic potentials, the van der Waals barrier, and a complex band analysis are also examined for a thorough understanding of Esaki diodes.

74 ATOMIC AND MOLECULAR PHYSICS↗

Superconducting (Ba,K)Fe 2 As 2 epitaxial films on single and bicrystal SrTiO 3 substrates

The realization of single crystal and bicrystal films of superconducting materials is of great interest because they allow the investigation of the intragrain performance as well as the understanding of potential limitations in the grain boundary transparency. For many years, the realization of a high-quality (Ba,K)Fe 2 As 2 film has been challenging. Here, the realization of (Ba,K)Fe 2 As 2 epitaxial thin films on single crystal SrTiO 3 (001) and [001]-tilt-type SrTiO 3 bicrystal substrates with high superconducting properties is demonstrated. The epitaxial growth of (Ba,K)Fe 2 As 2 was enabled by implementing an undoped BaFe 2 As 2 buffer layer between the SrTiO 3 substrate and (Ba,K)Fe 2 As 2 film. The film exhibits a high T c of 38.0 K and an extremely high J c of 14.3 MA/cm 2 at 4.2 K. Artificial grain boundaries of (Ba,K)Fe 2 As 2 were also successfully achieved on bicrystals with misorientation angles up to 36.8° by the same preparation methods. The artificial grain boundaries exhibited an identical T c of 38.0 K and an excellent transfer of the grain orientation from the bicrystal substrates with high crystallinity comparable to that of the high-quality Ba(Fe,Co) 2 As 2 films. Furthermore, this enables the investigation of the intrinsic (Ba,K)Fe 2 As 2 grain boundary nature, which will clarify its potential for superconducting applications, like Josephson junctions, wires, and magnets.

(Ba,K)Fe2As2↗

Bridging the gap between molecules and materials in quantum chemistry with localized active spaces

The number of materials that “bridge the gap” between single molecules and extended solids, such as metal-organic frameworks and organic semiconductors, has been increasing. Consequently, there is a growing need for modeling approaches that effectively integrate the real-space molecular perspective employed by computational chemists and the reciprocal-space dispersive perspective employed by computational physicists. Here, we propose the localized active space (LAS) approach as a promising method to successfully bridge this gap. The LAS approach extends the active space concept from multiconfigurational methods such as complete active space self-consistent field theory to multiple molecular fragments via a product-form wave function ansatz. Here, we apply this method to solid state phenomena by treating each unit cell as a fragment with different sets of local quantum numbers (e.g., charge and excitation number). State interaction between these LAS states (LASSI) thus provides a comprehensive basis for the study of charge and energy transfer, meeting and surpassing the capabilities of single-reference fragmentation approaches such as constrained density functional theory (cDFT). Most centrally, we show how combining this LASSI approach with multiconfigurational pair-density functional theory (MC-PDFT) provides an elegant and efficient method to compute band structures that capture multiconfigurational character. We apply the LASSI band structure approach to the computation of band gaps in stretched hydrogen chain, polyacetylene, and bulk nickel oxide (NiO), finding good or excellent quantitative agreement with reference values in all cases. Additionally, we use the LAS basis in one-dimensional model systems to demonstrate its ability to treat difficult solid-state phenomena such as exciton transfer and excitation at p-n junctions.

method development↗

Adverse Neurological Effects of Wildfire Smoke

The respiratory and cardiovascular effects of smoke exposure are well documented from cigarette smoking and particulate matter (PM) associated with air-pollution studies, but epidemiological data also suggests exposure to high levels of woodsmoke correlate with central-nervous-system (CNS) dysfunction, including elevated rates of Alzheimer’s disease (AD) and dementia. Neuro-inflammation is believed to initiate the majority of Alzheimer’s and other neurodegenerative diseases attributed to environmental factors. We investigated whether inhaled PM and specific classes of compounds in wildfire smoke condensate extract (WSE) reach the brain and cause neuro-inflammation that can lead to progressive neurological degeneration, using isotope tracing of labeled particulate matter and major compound classes, biomarkers of blood-brain barrier (BBB) integrity, and biomarkers of neuro-inflammation. This project showed that inhalation exposure to PM and major compound classes present in WSE reached the brain through absorption in the nasal cavity and systemic circulation across the BBB. Twenty-four exposures of WSE to brain endothelial cells that form the main physical barrier of the BBB produced dose-dependent increases in biomarkers of inflammation and decreases in tight junction markers between cells. Intranasal exposure to WSE caused inflammatory disfunction in lung and brain. Biomarkers of inflammation increased and an enzyme inhibiting inflammation decreased. Similar patterns of chemical-induced changes in the lung and brain suggest either: (1) chemicals may act through shared molecular pathways upon entering lung and brain, or (2) that mediators originating in the lung circulate systemically to the brain and drive neuroinflammation. These findings warrant further mechanistic studies to delineate the temporal sequence of events to establish the lung-brain axis.

54 ENVIRONMENTAL SCIENCES↗

Symmetry Breaking Charge Transfer in DNA-Templated Perylene Dimer Aggregates

Molecular aggregates are of interest to a broad range of fields including light harvesting, organic optoelectronics, and nanoscale computing. In molecular aggregates, nonradiative decay pathways may emerge that were not present in the constituent molecules. Such nonradiative decay pathways may include singlet fission, excimer relaxation, and symmetry-breaking charge transfer. Singlet fission, sometimes referred to as excitation multiplication, is of great interest to the fields of energy conversion and quantum information. For example, endothermic singlet fission, which avoids energy loss, has been observed in covalently bound, linear perylene trimers and tetramers. In this work, the electronic structure and excited-state dynamics of dimers of a perylene derivative templated using DNA were investigated. Specifically, DNA Holliday junctions were used to template the aggregation of two perylene molecules covalently linked to a modified uracil nucleobase through an ethynyl group. The perylenes were templated in the form of monomer, transverse dimer, and adjacent dimer configurations. The electronic structure of the perylene monomers and dimers were characterized via steady-state absorption and fluorescence spectroscopy. Initial insights into their excited-state dynamics were gleaned from relative fluorescence intensity measurements, which indicated that a new nonradiative decay pathway emerges in the dimers. Femtosecond visible transient absorption spectroscopy was subsequently used to elucidate the excited-state dynamics. A new excited-state absorption feature grows in on the tens of picosecond timescale in the dimers, which is attributed to the formation of perylene anions and cations resulting from symmetry-breaking charge transfer. Given the close proximity required for symmetry-breaking charge transfer, the results shed promising light on the prospect of singlet fission in DNA-templated molecular aggregates.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Structural Insight into a Sixteen Cyanine Dye Construct via Exciton–Exciton Annihilation

Molecular (dye) aggregates play a prominent role in light harvesting and are of interest in quantum information science; however, there are limited reports hat programmably assemble many (>4) dye aggregates featuring strong coupling and exciton delocalization. Using oligonucleotides with four Cy5s covalently linked in series along the phosphate backbone, we bring four, eight, and sixteen Cy5s in close proximity by assembling four-armed junctions. We elucidate their structure via gel electrophoresis and steady-state and transient optical spectroscopy. We find that Cy5 has a strong propensity to form tetramer clusters, where the exciton is delocalized over all four Cy5s, that the exciton is not delocalized beyond tetramer clusters in the eight and sixteen Cy5 constructs, and that the sixteen Cy5 construct may consist of pairs of tetramer clusters that are isolated from one another. Many-dye aggregates such as these may serve useful as antennae for their intense light absorption and spatially directed energy transfer.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗