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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 163 records · Page 9
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Toward autonomous design and synthesis of novel inorganic materials

Autonomous experimentation driven by artificial intelligence (AI) provides an exciting opportunity to revolutionize inorganic materials discovery and development. Herein, we review recent progress in the design of self-driving laboratories, including robotics to automate materials synthesis and characterization, in conjunction with AI to interpret experimental outcomes and propose new experimental procedures. We focus on efforts to automate inorganic synthesis through solution-based routes, solid-state reactions, and thin film deposition. In each case, connections are made to relevant work in organic chemistry, where automation is more common. Characterization techniques are primarily discussed in the context of phase identification, as this task is critical to understand what products have formed during synthesis. The application of deep learning to analyze multivariate characterization data and perform phase identification is examined. To achieve “closed-loop” materials synthesis and design, we further provide a detailed overview of optimization algorithms that use active learning to rationally guide experimental iterations. Lastly, we highlight several key opportunities and challenges for the future development of self-driving inorganic materials synthesis platforms.

36 MATERIALS SCIENCE↗
DOE OSTI2024

De novo design of buttressed loops for sculpting protein functions

In natural proteins, structured loops have central roles in molecular recognition, signal transduction and enzyme catalysis. However, because of the intrinsic flexibility and irregularity of loop regions, organizing multiple structured loops at protein functional sites has been very difficult to achieve by de novo protein design. Here we describe a solution to this problem that designs tandem repeat proteins with structured loops (9–14 residues) buttressed by extensive hydrogen bonding interactions. Experimental characterization shows that the designs are monodisperse, highly soluble, folded and thermally stable. Crystal structures are in close agreement with the design models, with the loops structured and buttressed as designed. We demonstrate the functionality afforded by loop buttressing by designing and characterizing binders for extended peptides in which the loops form one side of an extended binding pocket. The ability to design multiple structured loops should contribute generally to efforts to design new protein functions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Testing, Calibration, and UxS Integration of the Kromek GR1 Plus CZT Gamma Spectrometer

Collecting radiation measurements can be a hazardous task, especially in the presence of highly active sources. Various scenarios necessitate source search, classification, and quantification, often with limited or no a priori information. Activities such as disaster mitigation, emergency response, environmental monitoring, and site remediation may involve dangerous radioactive sources. In these situations, there is a pressing need for remote monitoring capabilities that protect human operators from potential harm and enhance adherence to the principle of “As Low as Reasonably Achievable” (ALARA) for radiation doses. The first step toward achieving remote radiation measurement capabilities is the remote operation of a radiation sensor. Once this milestone is reached, the next challenge is to integrate this remote sensing capability into suitable actuation agents, collectively referred to as uncrewed systems (UxS). These systems include familiar platforms such as robotic quadrupeds, aerial multirotor vehicles, and ground vehicles, any of which may be teleoperated, act autonomously, or utilize a combination of both. A critical factor in achieving remote radiation sensing is the availability of data from the appropriate sensor. Many commercially available radiation sensors have closed-source documentation for their communication protocols. Typical end-user products are often self-contained, handheld devices designed for manual measurement scenarios. While there are commercial off-the-shelf (COTS) integrations of radiation sensors with UxS available for purchase, these solutions are typically tailored for specific use cases and may not meet the requirements of different applications. This paper discusses efforts to remotely acquire radiation measurements from a small form-factor CZT gamma spectrometer. Sandia National Laboratories has successfully demonstrated the initial capability to integrate low size, weight, and power (SWaP) gamma spectroscopy into various UxS, alongside co-located GPS data logging and sensor calibration and qualification. With remote gamma spectroscopy achieved, the stage is set for UxS integration of this capability.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
DOE OSTI2023

A Minkowski difference-based advancing front packing technique for generating convex noncircular particles in complex domains

In this work, a Minkowski difference-based advancing front approach is proposed to generate convex and non-circular particles in a predefined computational domain. Two specific algorithms are developed to handle the contact conformity of generated particles with the boundaries of the computational domain. The first, called the open form, is used to handle the smooth contact of generated particles with (external) boundaries, while the other, called the closed form, is proposed to handle the internal boundaries of a computational domain with a complex cavity. The Gilbert-Johnson-Keerthi (GJK) method is used to efficiently solve the contact detection between the newly generated particle at the front and existing particles. Furthermore, the problem of one-sided particle lifting, which can cause some defects in the packing structure in existing advancing front methods during packing generation, is highlighted and an effective solution is developed. Several examples of increasing complexity are used to demonstrate the efficiency and applicability of the proposed packing generation approach. The numerical results show that the generated packing is not only more uniform, but also achieves a higher packing density than existing advancing front methods.

42 ENGINEERING↗
DOE OSTI2024

Watching a signaling protein function: What has been learned over four decades of time-resolved studies of photoactive yellow protein

Photoactive yellow protein (PYP) is a signaling protein whose internal p-coumaric acid chromophore undergoes reversible, light-induced trans-to-cis isomerization, which triggers a sequence of structural changes that ultimately lead to a signaling state. Since its discovery nearly 40 years ago, PYP has attracted much interest and has become one of the most extensively studied proteins found in nature. The method of time-resolved crystallography, pioneered by Keith Moffat, has successfully characterized intermediates in the PYP photocycle at near atomic resolution over 12 decades of time down to the sub-picosecond time scale, allowing one to stitch together a movie and literally watch a protein as it functions. But how close to reality is this movie? To address this question, results from numerous complementary time-resolved techniques including x-ray crystallography, x-ray scattering, and spectroscopy are discussed. Emerging from spectroscopic studies is a general consensus that three time constants are required to model the excited state relaxation, with a highly strained ground-state cis intermediate formed in less than 2.4 ps. Persistent strain drives the sequence of structural transitions that ultimately produce the signaling state. Crystal packing forces produce a restoring force that slows somewhat the rates of interconversion between the intermediates. Moreover, the solvent composition surrounding PYP can influence the number and structures of intermediates as well as the rates at which they interconvert. When chloride is present, the PYP photocycle in a crystal closely tracks that in solution, which suggests the epic movie of the PYP photocycle is indeed based in reality.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Light-induced protein structural dynamics in bacteriophytochrome revealed by time-resolved x-ray solution scattering

Bacteriophytochromes (BphPs) are photoreceptors that regulate a wide range of biological mechanisms via red light–absorbing (Pr)–to–far-red light–absorbing (Pfr) reversible photoconversion. The structural dynamics underlying Pfr-to-Pr photoconversion in a liquid solution phase are not well understood. We used time-resolved x-ray solution scattering (TRXSS) to capture light-induced structural transitions in the bathy BphP photosensory module of Pseudomonas aeruginosa. Kinetic analysis of the TRXSS data identifies three distinct structural species, which are attributed to lumi-F, meta-F, and Pr, connected by time constants of 95 μs and 21 ms. Structural analysis based on molecular dynamics simulations shows that the light activation of PaBphP accompanies quaternary structural rearrangements from an “II”-framed close form of the Pfr state to an “O”-framed open form of the Pr state in terms of the helical backbones. This study provides mechanistic insights into how modular signaling proteins such as BphPs transmit structural signals over long distances and regulate their downstream biological responses.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2025

Dataset for: Rooftop solar and energy storage programs can remediate energy-limiting behaviors of energy insecure households

Energy insecurity affects most low-income households in the United States. Energy insecurity, which is characterized by a household’s inability to afford their energy needs, often leads to risky choices, causing other forms of insecurity including food and health. Although there are government programs designed to provide relief to low-income households that face energy insecurity, eligibility for these programs is usually determined by household income, and those with incomes close to the threshold face uncertainty or may be left out. In many cases, these households turn to energy-limiting behaviors as a strategy to lower their electric utility bills. This paper explores the relationship between energy insecurity and energy-limiting behaviors to investigate alternative solutions that target the households that may fall out of available energy assistance programs. We explore the role of battery energy storage systems and rooftop solar photovoltaics in improving energy affordability. The results show that residential rooftop solar and behind-the-meter energy storage can offset two-thirds of the bill savings that households attain through energy-limiting behavior. Household renewable energy systems could complement existing energy assistance programs to provide long-term bill relief, enabling occupants to live in their homes with comfort and dignity. This dataset is intended to allow readers to reproduce and customize the analysis performed in this work to their benefit.

Kerby, Jessica [Pacific Northwest National Laborat↗
DOE OSTI2025

Coordination Chemistry and Photoluminescence of Sm(II) Dibenzo-24-crown-8 Complexes

Three Sm(II) dibenzo-24-crown-8 (db24c8) complexes were synthesized in anhydrous, air-free conditions via the reaction of SmI 2 with db24c8 and tetrabutylammonium tetraphenylborate ([TBA][BPh 4 ]; where needed) in acetonitrile (CH 3 CN), dimethoxyethane (DME), and tetrahydrofuran (THF) to yield [Sm(db24c8)(CH 3 CN) 2 ][BPh 4 ][I]·CH 3 CN, [Sm(db24c8)(DME)]I 2 , and [Sm(db24c8)(THF) 2 ]I 2 , respectively. In each case, a 10-coordinate, staggered dodecahedral (2:6:2) environment is formed around the Sm 2+ center that is completed by either two solvent molecules (CH 3 CN or THF) or one bidentate solvent molecule (DME). Inner-sphere solvent molecules can be excluded by reacting SmI 2 with db24c8 in 1:3 THF:toluene to yield Sm(db24c8)I 2 . Here, this molecule features a distorted, eight-coordinate, hexagonal pyramidal Sm 2+ metal center, where the coordinated db24c8 molecule shows a torsion angle unexpectedly close to the 180° antiperiplanar arrangement and two uncoordinated db24c8 oxygen atoms. Solution UV–vis–NIR measurements demonstrate that Sm 2+ is a good size match for the cavity of various db24c8 conformations and that Eu 2+ and Yb 2+ exhibit competition between acetonitrile solvation and the Eu 2+ and Yb 2+ /db24c8 complexes in solution. During excitation by 546 nm light, both [Sm(db24c8)(DME)]I 2 and [Sm(db24c8)(THF) 2 ]I 2 exhibit mixed 5d → 4f and 4f → 4f emission at 20 °C and exclusively 4f → 4f at −180 °C, whereas Sm(db24c8)I 2 only shows 5d → 4f emission regardless of temperature. Photoluminescence from [Sm(db24c8)(CH 3 CN) 2 ][BPh 4 ][I]·CH 3 CN is quenched.

Cations↗
DOE OSTI2024

Characterization of partial wetting by CMAS droplets using multiphase many-body dissipative particle dynamics and data-driven discovery based on PINNs

The molten sand that is a mixture of calcia, magnesia, alumina and silicate, known as CMAS, is characterized by its high viscosity, density and surface tension. The unique properties of CMAS make it a challenging material to deal with in high-temperature applications, requiring innovative solutions and materials to prevent its buildup and damage to critical equipment. Here, we use multiphase many-body dissipative particle dynamics simulations to study the wetting dynamics of highly viscous molten CMAS droplets. The simulations are performed in three dimensions, with varying initial droplet sizes and equilibrium contact angles. We propose a parametric ordinary differential equation (ODE) that captures the spreading radius behaviour of the CMAS droplets. The ODE parameters are then identified based on the physics-informed neural network (PINN) framework. Subsequently, the closed-form dependency of parameter values found by the PINN on the initial radii and contact angles are given using symbolic regression. Finally, we employ Bayesian PINNs (B-PINNs) to assess and quantify the uncertainty associated with the discovered parameters. In brief, this study provides insight into spreading dynamics of CMAS droplets by fusing simple parametric ODE modelling and state-of-the-art machine-learning techniques.

Mechanics↗
DOE OSTI2020

Technical Performance of Refractory Liners for Molten Chloride Salt Thermal Energy Storage Systems

A chloride-based molten-salt system that uses a ternary blend of MgCl2/KCl/NaCl is investigated to provide higher temperature thermal energy storage capability. Despite higher thermal stability, molten chlorides present several unique challenges, including the design of internal refractory-ceramic liners to prevent the corrosion and thermal stress of alloy tank shells. This work discusses issues and potential solutions related to containment of molten chloride salt, specifically the optimization of the refractory material at the molten salt interface (hot face). The down-selected hot face candidate limits permeation of salt through the material and forms a highly stable secondary surface phase in equilibrium with the molten salt. A mortar is created using the corrosion resistant hot face brick. Brick and mortar composite are subjected to mechanical stress/strain analysis, in order to calculate composite material properties and better inform thermomechanical models. The U.S. Department of Energy Generation 3 (DOE Gen3) program seeks to develop higher efficiency CSP plants that can provide cost-competitive, flexible power in the U.S. electric grid. The proposed Gen3 Liquid Pathway CSP plant closely resembles the configuration of current nitrate salt power towers with two-tank storage (Gen2). The differences between Gen2 and Gen3 include the types of compatible materials used in salt storage tank construction. Stainless steel loses strength at Gen3 temperatures, and although nickel superalloys would be capable of withstanding sustained high temperatures, these materials are prohibitively expensive at scale. Uninsulated tank shells also pose a significant risk as common steels are highly susceptible to chemical attack from molten chloride salt. To address these concerns, refractory-ceramic based containment materials are proposed to line the inside of the hot and cold storage tanks. In doing so, stainless or carbon steel shells may be used in construction depending on the level of insulation provided. The composition of the internal liner requires careful consideration to maximize the efficacy of multiple parameters including corrosion resistance, strength at operating temperature, durability, and cost. This is particularly true for the material at the interface with the salt, known as the "hot face", which is responsible for protecting the insulating layers between the tank shell and the hot face brick layer. The molten salt in this system is superheated over 300 °C above its freeze temperature. Therefore, unlike other industrial processes which use refractory-lined vessels, it is not expected that a freeze plane will develop in the hot face. Therefore, the hot face must be designed to withstand chemical corrosion and inhibit permeation of molten salt into the insulating layers. A down selection was performed to identify a hot face candidate best equipped to maintain thermal, mechanical, and chemical integrity when exposed to molten salt over extended periods of time. Long-duration chemical capability experiments were conducted with the down selected hot face refractory fully immersed in molten chloride salt for up to 3000 hours. The average salt penetration does not exceed 100 microns. When extrapolated to 20 and 30 years of continuous exposure, the expected salt penetration depth is approximately 2.0 mm and 2.9 mm, respectively. A magnesium-rich secondary phases develops at the salt/refractory interface. X-ray diffraction identifies the material as forsterite (Mg2SiO4), which is reported to form synthetically in molten chloride salt solutions. These results suggest the selected hot face will adequately inhibit salt permeation. While there is optimism that the hot face brick will inhibit salt permeation, mortar joints are typically the weakest point of a refractory brick liner. From a thermochemical perspective, differing thermal expansion coefficients may result in the mortar and brick to grow independent of each other, creating gaps through which molten salt can penetrate. To address this issue, NREL has developed an in-house mortar composed of the down selected hot face brick that has been shown to be compatible with the salt. Compressive stress/strain analyses have been performed on the brick/ mortar composites to generate stress/strain curves. Modulus of elasticity and Poisson's ratio of the composite may be calculated from the stress/strain curves, in order to provide more representative data to finite element mechanical models for accurate approximation of stress on the tank shell and the amount of thermal expansion expected within the tank liner.

41 EE - Solar Energy Technologies Office (EE-4S)↗
DOE OSTI2020

Convex Programs for Minimal-Area Problems

The minimal-area problem that defines string diagrams in closed string field theory asks for the metric of least area on a Riemann surface with the condition that all non-contractible closed curves have length at least 2π. This is an extremal length problem in conformal geometry as well as a problem in systolic geometry. Here, we consider the analogous minimal-area problem for homology classes of curves and, with the aid of calibrations and the max flow-min cut theorem, formulate it as a local convex program. We derive an equivalent dual program involving maximization of a concave functional. These two programs give new insights into the form of the minimal-area metric and are amenable to numerical solution. We explain how the homology problem can be modified to provide the solution to the original homotopy problem.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2021

On the implementation of dislocation reactions in continuum dislocation dynamics modeling of mesoscale plasticity

The continuum dislocation dynamics framework for mesoscale plasticity is intended to capture the dislocation density evolution and the deformation of crystals when subjected to mechanical loading. It does so by solving a set of transport equations for dislocations concurrently with crystal mechanics equations, with the latter being cast in the form of an eigenstrain problem. Incorporating dislocation reactions in the dislocation transport equations is essential for making such continuum dislocation dynamics predictive. A formulation is proposed to incorporate dislocation reactions in the transport equations of the vector density-based continuum dislocation dynamics. This formulation aims to rigorously enforce dislocation line continuity using the concept of virtual dislocations that close all dislocation loops involved in cross slip, annihilation, and glissile and sessile junction reactions. The addition of virtual dislocations enables us to accurately enforce the divergence free condition upon the numerical solution of the dislocation transport equations for all slip systems individually. A set of tests were performed to illustrate the accuracy of the formulation and the solution of the transport equations within the vector density-based continuum dislocation dynamics. Comparing the results from these tests with an earlier approach in which the divergence free constraint was enforced on the total dislocation density tensor or the sum of two densities when only cross slip is considered shows that the new approach yields highly accurate results. Bulk simulations were performed for a face centered cubic crystal based on the new formulation and the results were compared with discrete dislocation dynamics predictions of the same. The microstructural features obtained from continuum dislocation dynamics were also analyzed with reference to relevant experimental observations.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Review: Magnesium Sheet Alloy Development for Room Temperature Forming

Sheet metal forming operations in the automotive industry, including stamping, flanging, bending, hemming and trimming, are dominantly done at room temperature (RT). Unfortunately, the poor RT formability of magnesium due to its hexagonal close packed (HCP) structure and generally strong texture has limited the use of these processes in high-volume automotive production. However, the formability of magnesium can be improved via fine grain structure and random texture to enable some RT forming operations. Here, this paper presents the latest magnesium alloy development and evaluation by the United States Automotive Materials Partnership (USAMP) in collaboration with its university partners. A new sheet alloy developed in a recent USAMP project, ZAXME11100 (USAMP Alloy 2 Plus), offers excellent ductility (31% tensile elongation) and RT formability (7.8 mm Erichsen Index) in solution-treated condition (T4), and a high yield strength (270 MPa) upon post-forming aging treatment (T6), promising RT forming for automotive applications.

36 MATERIALS SCIENCE↗
DOE OSTI2020

A Computational Assessment of Actinide Dioxide Cations AnO 2 2+ for An = U to Lr: The Limited Stability Range of the Hexavalent Actinyl Moiety, [O=An=O] 2+

The isolated gas-phase actinide dioxide dications, AnO 2 2+ , were evaluated by DFT and coupled cluster CCSD(T) calculations for 12 actinides, An = U–Lr. CASSCF calculations were used to define the orbitals for the CCSD(T) calculations. The characteristic linear [O$=$An$=$O] 2+ hexavalent actinyl(VI) was found to be the lowest energy structure for An = U, Np, and Pu, which also form stable actinyl(VI) species in solution and possibly for Am when spin–orbit effects are included. For Am, there is a divalent [An II (O 2 )] 2+ structure where the dioxygen is an end-on physisorbed η 1 - 3 O 2 2 kcal/mol above the actinyl when spin–orbit effects are included which lower the energy of the actinyl structure. For An = Cm, Bk, and Lr, the lowest energy structure is trivalent [An III (O 2 – )] 2+ where the dioxygen is a side-on superoxide, η 2 -O 2 – . For Cm, the actinyl is close in energy to the ground state when spin–orbit effects are included. For An = Cf, Es, Fm, Md, and No, the lowest energy structure is divalent [An II (O 2 )] 2+ where the dioxygen is an end-on physisorbed η 1 - 3 O 2 . The relative energies suggest that curyl(VI) and berkelyl(VI), like well-known americyl(VI), might be stabilized by coordinating ligands in condensed phases. The results further indicate that for californyl and beyond, the actinyl(VI) moieties will probably be elusive even using strong donor ligands. The prevalence of low oxidation states (OSs) An(II) and An(III) for transplutonium actinides reflects stabilization of the 5f orbitals and validates established trends, including the remarkably high stability of divalent No. Finally, bond distances and other parameters suggest maximum bond covalency around plutonyl(VI), with a particularly substantial decrease in bond strength between americyl(VI) and curyl(VI).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

A multistage distributionally robust optimization approach to water allocation under climate uncertainty

This paper investigates a Multistage Distributionally Robust Optimization (MDRO) approach to water allocation under climate uncertainty. The MDRO is formed by creating sets of conditional distributions (called conditional ambiguity sets) on a finite scenario tree. The distributions in the conditional ambiguity sets remain close to a nominal conditional distribution according a ø-divergence (e.g., Kullback-Leibler divergence, Hellinger distance, Burg entropy, etc.). Here, the paper discusses a decomposition algorithm to solve the resulting MDRO with ø-divergences, which uses the dual formulation and solves only linear subproblems instead of convex ones. Some properties of the algorithm such as generating feasible policies and valid upper/lower bounds are established. The paper then applies the modeling and solution techniques to allocate water in a rapidly-developing area of Tucson, Arizona. Tucson, like many arid and semi-arid regions around the world, faces considerable uncertainty in its ability to provide water for its citizens in the future. The primary sources of uncertainty in the Tucson region include (1) unpredictable population growth, (2) the availability of water from the Colorado River, and (3) the effects of climate variability on water consumption. This paper integrates forecasts for all these sources of uncertainty into a single optimization model for robust and sustainable water allocation. Then, it uses this model to analyze the value of constructing additional treatment facilities to reduce future water shortages. The results indicate that the MDRO approach can be very valuable for water managers by providing insights to minimize their risks and help them plan for the future.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2023

Design of Diverse Asymmetric Pockets in De Novo Homo-oligomeric Proteins

A challenge for design of protein–small-molecule recognition is that incorporation of cavities with size, shape, and composition suitable for specific recognition can considerably destabilize protein monomers. This challenge can be overcome through binding pockets formed at homo-oligomeric interfaces between folded monomers. Interfaces surrounding the central homo-oligomer symmetry axes necessarily have the same symmetry and so may not be well suited to binding asymmetric molecules. To enable general recognition of arbitrary asymmetric substrates and small molecules, we developed an approach to designing asymmetric interfaces at off-axis sites on homo-oligomers, analogous to those found in native homo-oligomeric proteins such as glutamine synthetase. We symmetrically dock curved helical repeat proteins such that they form pockets at the asymmetric interface of the oligomer with sizes ranging from several angstroms, appropriate for binding a single ion, to up to more than 20 Å across. Of the 133 proteins tested, 84 had soluble expression in E. coli, 47 had correct oligomeric states in solution, 35 had small-angle X-ray scattering (SAXS) data largely consistent with design models, and 8 had negative-stain electron microscopy (nsEM) 2D class averages showing the structures coming together as designed. Both an X-ray crystal structure and a cryogenic electron microscopy (cryoEM) structure are close to the computational design models. The nature of these proteins as homo-oligomers allows them to be readily built into higher-order structures such as nanocages, and the asymmetric pockets of these structures open rich possibilities for small-molecule binder design free from the constraints associated with monomer destabilization.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2024

Uncovering the binding nature of thiocyanate in contact ion pairs with lithium ions

Ion pair formation is a fundamental molecular process that occurs in a wide variety of systems, including electrolytes, biological systems, and materials. In solution, the thiocyanate (SCN–) anion interacts with cations to form contact ion pairs (CIPs). Due to its ambidentate nature, thiocyanate can bind through either its sulfur or nitrogen atoms, depending on the solvent. This study focuses on the binding nature of thiocyanate with lithium ions as a function of the solvents using FTIR, 2D infrared spectroscopy (2DIR) spectroscopies, and theoretical calculations. The study reveals that the SCN– binding mode (S or N end) in CIPs can be identified through 2DIR spectroscopy but not by linear IR spectroscopy. Linear IR spectroscopy shows that the CN stretch frequencies are too close to one another to separate N- and S-bound CIPs. Moreover, the IR spectrum shows that the S–C stretch presents different frequencies for the salt in different solvents, but it is related to the anion speciation rather than to its binding mode. A similar trend is observed for the anion bend. 2DIR spectra show different dynamics for N-bound and S-bound thiocyanate. In particular, the frequency–frequency correlation function (FFCF) dynamics extracted from the 2DIR spectra have a single picosecond exponential decay for N-bound thiocyanate and a biexponential decay for S-bound thiocyanate, consistent with the binding mode of the anion. Lastly, it is also observed that the binding mode also affects the line shape parameters, probably due to the different molecular mechanisms of the FFCF for N- and S-bound CIPs.

25 ENERGY STORAGE↗
DOE OSTI2020

A Metal-on-Metal Growth Approach to Metal–Metal Oxide Core–Shell Nanostructures with Plasmonic Properties

Hybrid core–shell nanoparticles integrate the material properties from individual components; however, the synthesis of core–shell nanoparticles with dissimilar materials remains challenging. Herein, we applied a metal-on-metal thin film growth approach to control the conformal deposition of non-precious metal shells on the Cu-based metal cores to form core–shell structures of metal–metal oxide hybrids (M–M'O x , where M = AuCu 3 or Cu, M' = Fe, Mn, and Ni). The deposition kinetics were controlled by a temperature-regulated thermal decomposition of zerovalent transition metal complexes. It is predicted that the conformal deposition can be promoted by keeping the initial deposition temperature close to the thermal decomposition temperature of the zerovalent precursors. The mechanisms of strain reduction and interdiffusion facilitate conformal deposition over island growth in the synthesis with slow reaction kinetics. This study provides insightful guidance to metal-on-metal growth in solution at the nanoscale and thus the seed-mediated approach to hybrid core–shell structures. The optical properties of these metal–metal oxide hybrids were investigated experimentally and interpreted by theoretical simulations. Despite damping effects, the plasmonic properties of these Cu-based core-metal oxide shell structures may have the potential to enable plasmon-enhanced applications.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗