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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 469 records · Page 26
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Force-Free Identification of Minimum-Energy Pathways and Transition States for Stochastic Electronic Structure Theories

Here, the accurate mapping of potential energy surfaces (PESs) is crucial to our understanding of the numerous physical and chemical processes mediated by atomic rearrangements, such as conformational changes and chemical reactions, and the thermodynamic and kinetic feasibility of these processes. Stochastic electronic structure theories, e.g., Quantum Monte Carlo (QMC) methods, enable highly accurate total energy calculations that in principle can be used to construct the PES. However, their stochastic nature poses a challenge to the computation and use of forces and Hessians, which are typically required in algorithms for minimum-energy pathway (MEP) and transition state (TS) identification, such as the nudged elastic band (NEB) algorithm and its climbing image formulation. Here, we present strategies that utilize the surrogate Hessian line-search method, previously developed for QMC structural optimization, to efficiently identify MEP and TS structures without requiring force calculations at the level of the stochastic electronic structure theory. By modifying the surrogate Hessian algorithm to operate in path-orthogonal subspaces and at saddle points, we show that it is possible to identify MEPs and TSs by using a force-free QMC approach. We demonstrate these strategies via two examples, the inversion of the ammonia (NH 3 ) molecule and the nucleophilic substitution (S N 2) reaction F – + CH 3 F → FCH 3 + F – . We validate our results using Density Functional Theory (DFT)- and Coupled Cluster (CCSD, CCSD(T))-based NEB calculations. We then introduce a hybrid DFT-QMC approach to compute thermodynamic and kinetic quantities, free energy differences, rate constants, and equilibrium constants that incorporates stochastically optimized structures and their energies, and show that this scheme improves upon DFT accuracy. Our methods generalize straightforwardly to other systems and other high-accuracy theories that similarly face challenges computing energy gradients, paving the way for highly accurate PES mapping, transition state determination, and thermodynamic and kinetic calculations at significantly reduced computational expense.

Iyer, Gopal R.↗
DOE OSTI2023

Magic Numbers and Stabilities of Photoionized Water Clusters: Computational and Experimental Characterization of the Nanosolvated Hydronium Ion

The stability and distributions of small water clusters generated in a supersonic beam expansion are interrogated by tunable vacuum ultraviolet (VUV) radiation generated at a synchrotron. Time-of-flight mass spectrometry reveals enhanced population of various protonated water clusters (H + (H 2 O) $n$ ) based upon ionization energy and photoionization distance from source, suggesting there are "magic" numbers below the traditional $n$ = 21 that predominates in the literature. These intensity distributions suggest that VUV threshold photoionization (11.0-11.5 eV) of neutral water clusters close to the nozzle exit leads to a different nonequilibrium state compared to a skimmed molecular beam. This results in the appearance of a new magic number at 14. Metadynamics conformer searches coupled with modern density functional calculations are used to identify the global minimum energy structures of protonated water clusters between $n$ = 2 and 21, as well as the manifold of low-lying metastable minima. New lowest energy structures are reported for the cases of $n$ = 5, 6, 11, 12, 16, and 18, and special stability is identified by several measures. These theoretical results are in agreement with the experiments performed in this work in that $n$ = 14 is shown to exhibit additional stability, based on the computed second-order stabilization energy relative to most cluster sizes, though not to the extent of the well-known $n$ = 21 cluster. Other cluster sizes that show some additional energetic stability are $n$ = 7, 9, 12, 17, and 19. To gain insight into the balance between ion-water and water-water interactions as a function of the cluster size, an analysis of the effective two-body interactions (which sum exactly to the total interaction energy) was performed. In conclusion, this analysis reveals a crossover as a function of cluster size between a water-hydronium-dominated regime for small clusters and a water-water-dominated regime for larger clusters around $n$ = 17.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Probing the Atomic-Scale Structure of Amorphous Aluminum Oxide Grown by Atomic Layer Deposition

Atomic layer deposition (ALD) is a well-established technique for depositing nanoscale coatings with pristine control of film thickness and composition. The trimethylaluminum (TMA) and water (H 2 O) ALD chemistry is inarguably the most widely used and yet to date, we have little information about the atomic-scale structure of the amorphous aluminum oxide (AlO x ) formed by this chemistry. This lack of understanding hinders our ability to establish process-structure-property relationships and ultimately limits technological advancements employing AlOx made via ALD. In this work, we employ synchrotron high-energy X-ray diffraction (HE-XRD) coupled with pair distribution function (PDF) analysis to characterize the atomic structure of amorphous AlO x ALD coatings. We combine ex situ and in operando HE-XRD measurements on ALD AlO x and fit these experimental data using stochastic structural modeling to reveal variations in the Al-O bond length, Al and O coordination environment, and extent of Al vacancies as a function of growth conditions. In particular, the local atomic structure of ALD AlO x is found to change with the substrate and number of ALD cycles. The observed trends are consistent with the formation of bulk Al 2 O 3 surrounded by an O-rich surface layer. We deconvolute these data to reveal atomic-scale structural information for both the bulk and surface phases. Overall, this work demonstrates the usefulness of HE-XRD and PDF analysis in improving our understanding of the structure of amorphous ALD thin films and provides a pathway to evaluate how process changes impact the structure and properties of ALD films.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Alloying–realloying enabled high durability for Pt–Pd-3d-transition metal nanoparticle fuel cell catalysts

Abstract Alloying noble metals with non-noble metals enables high activity while reducing the cost of electrocatalysts in fuel cells. However, under fuel cell operating conditions, state-of-the-art oxygen reduction reaction alloy catalysts either feature high atomic percentages of noble metals (>70%) with limited durability or show poor durability when lower percentages of noble metals (<50%) are used. Here, we demonstrate a highly-durable alloy catalyst derived by alloying PtPd (<50%) with 3d-transition metals (Cu, Ni or Co) in ternary compositions. The origin of the high durability is probed by in-situ/operando high-energy synchrotron X-ray diffraction coupled with pair distribution function analysis of atomic phase structures and strains, revealing an important role of realloying in the compressively-strained single-phase alloy state despite the occurrence of dealloying. The implication of the finding, a striking departure from previous perceptions of phase-segregated noble metal skin or complete dealloying of non-noble metals, is the fulfilling of the promise of alloy catalysts for mass commercialization of fuel cells.

25 ENERGY STORAGE↗
DOE OSTI2024

Spin-EPR-pair separation by conveyor-mode single electron shuttling in Si/SiGe

Long-ranged coherent qubit coupling is a missing function block for scaling up spin qubit based quantum computing solutions. Spin-coherent conveyor-mode electron-shuttling could enable spin quantum-chips with scalable and sparse qubit-architecture. Its key feature is the operation by only few easily tuneable input terminals and compatibility with industrial gate-fabrication. Single electron shuttling in conveyor-mode in a 420 nm long quantum bus has been demonstrated previously. Here we investigate the spin coherence during conveyor-mode shuttling by separation and rejoining an Einstein-Podolsky-Rosen (EPR) spin-pair. Compared to previous work we boost the shuttle velocity by a factor of 10000. We observe a rising spin-qubit dephasing time with the longer shuttle distances due to motional narrowing and estimate the spin-shuttle infidelity due to dephasing to be 0.7% for a total shuttle distance of nominal 560 nm. Shuttling several loops up to an accumulated distance of 3.36 μm, spin-entanglement of the EPR pair is still detectable, giving good perspective for our approach of a shuttle-based scalable quantum computing architecture in silicon.

42 ENGINEERING↗
DOE OSTI2024

Active learning of ternary alloy structures and energies

Abstract Machine learning models with uncertainty quantification have recently emerged as attractive tools to accelerate the navigation of catalyst design spaces in a data-efficient manner. Here, we combine active learning with a dropout graph convolutional network (dGCN) as a surrogate model to explore the complex materials space of high-entropy alloys (HEAs). We train the dGCN on the formation energies of disordered binary alloy structures in the Pd-Pt-Sn ternary alloy system and improve predictions on ternary structures by performing reduced optimization of the formation free energy, the target property that determines HEA stability, over ensembles of ternary structures constructed based on two coordinate systems: (a) a physics-informed ternary composition space, and (b) data-driven coordinates discovered by the Diffusion Maps manifold learning scheme. Both reduced optimization techniques improve predictions of the formation free energy in the ternary alloy space with a significantly reduced number of DFT calculations compared to a high-fidelity model. The physics-based scheme converges to the target property in a manner akin to a depth-first strategy, whereas the data-driven scheme appears more akin to a breadth-first approach. Both sampling schemes, coupled with our acquisition function, successfully exploit a database of DFT-calculated binary alloy structures and energies, augmented with a relatively small number of ternary alloy calculations, to identify stable ternary HEA compositions and structures. This generalized framework can be extended to incorporate more complex bulk and surface structural motifs, and the results demonstrate that significant dimensionality reduction is possible in thermodynamic sampling problems when suitable active learning schemes are employed.

Chemistry↗
DOE OSTI2024

From small changes to big gains: pyridinium-based tetralactam macrocycle for enhanced sugar recognition in water

The complex distribution of functional groups in carbohydrates, coupled with their strong solvation in water, makes them challenging targets for synthetic receptors. Despite extensive research into various molecular frameworks, most synthetic carbohydrate receptors have exhibited low affinities, and their interactions with sugars in aqueous environments remain poorly understood. In this work, we present a simple pyridinium-based hydrogen-bonding receptor derived from a subtle structural modification of a well-known tetralactam macrocycle. This small structural change resulted in a dramatic enhancement of glucose binding affinity, increasing from 56 M −1 to 3001 M −1 . Remarkably, the performance of our synthetic lectin surpasses that of the natural lectin, concanavalin A, by over fivefold. X-ray crystallography of the macrocycle–glucose complex reveals a distinctive hydrogen bonding pattern, which allows for a larger surface overlap between the receptor and glucose, contributing to the enhanced affinity. Furthermore, this receptor possesses allosteric binding sites, which involve chloride binding and trigger receptor aggregation. This unique allosteric process reveals the critical role of structural flexibility in this hydrogen-bonding receptor for the effective recognition of sugars. We also demonstrate the potential of this synthetic lectin as a highly sensitive glucose sensor in aqueous solutions.

Zhai, Canjia↗
DOE OSTI2025

Acidities of MgO surface sites: implications for the formation mechanism of Mg(OH) 2

The hydroxylation of periclase (MgO) to brucite (Mg(OH) 2 ) is thought to be an important intermediate step when using MgO to capture CO 2 from the atmosphere. However, the mechanism of hydroxylation of MgO to form Mg(OH) 2 is poorly understood. In this work, we used atomic-scale density functional tight binding simulations coupled with the metadynamics rare event method to analyze the surface chemistry of MgO and the acid dissociation equilibrium constants (pK a ) of its surface sites. The method and parameters were validated by calculating the pK a for hydroxylation of the first shell water bound to aqueous Mg 2+ ion. The pK a value derived using a probabilistic method was 12.3, which is in fair agreement with the accepted value of 11.4, with the difference between them equal to a ∼5 kJ mol −1 error in the calculations. We then extended these pK a calculations to probe the hydroxylation reactions of the surface sites of the MgO(100)–water interface, arriving at pK a s of 5.4 to deprotonate terminal water molecules bound to the surface magnesium sites (η-OH 2 or 〉MgOH 2 ), and 13.9 to deprotonate hydroxylated bridging oxygen sites (μ 5 -oxo or 〉O). Hydroxide (OH − ) adsorption on the surface was also probed and found to be less thermodynamically favorable than deprotonation of the terminal water molecule. The plausibility of the computed pK a s was verified using an activity-based speciation model and compared to pH measurements of water equilibrated with MgO nanoparticles and single crystals. The model predicted a solution pH of 7.1 when surface sites buffered and the pH of 12.0 when MgO dissolution dominated. These are close to the experimental initial solution pHs of 7–7.5 and the long term pHs of ∼10.5. The similarity suggests that the calculated pK a values from the DFTB+/metadynamics simulations are plausible and that these methods can be a useful tool to probe reaction mechanisms involving covalent bonds.

Adapa, Sai Krishna Reddy [Oak Ridge National Labor↗
DOE OSTI2022

Femtosecond intramolecular rearrangement of the CH 3 NCS radical cation

Strong-field ionization, involving tunnel ionization and electron rescattering, enables femtosecond time-resolved dynamics measurements of chemical reactions involving radical cations. Here, we compare the formation of CH 3 S + following the strong-field ionization of the isomers CH 3 SCN and CH 3 NCS. The former involves the release of neutral CN, while the latter involves an intramolecular rearrangement. Here, we find the intramolecular rearrangement takes place on a single picosecond timescale and exhibits vibrational coherence. Density functional theory and coupled-cluster calculations on the neutral and singly ionized species help us determine the driving force responsible for intramolecular rearrangement in CH 3 NCS. Our findings illustrate the complexity that accompanies radical cation chemistry following electron ionization and demonstrate a useful tool for understanding cation dynamics after ionization.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Stimulation of soil respiration by elevated CO 2 is enhanced under nitrogen limitation in a decade-long grassland study

Whether and how CO 2 and nitrogen (N) availability interact to influence carbon (C) cycling processes such as soil respiration remains a question of considerable uncertainty in projecting future C–climate feedbacks, which are strongly influenced by multiple global change drivers, including elevated atmospheric CO 2 concentrations (eCO 2 ) and increased N deposition. However, because decades of research on the responses of ecosystems to eCO 2 and N enrichment have been done largely independently, their interactive effects on soil respiratory CO 2 efflux remain unresolved. Here, we show that in a multifactor free-air CO 2 enrichment experiment, BioCON (Biodiversity, CO 2 , and N deposition) in Minnesota, the positive response of soil respiration to eCO 2 gradually strengthened at ambient (low) N supply but not enriched (high) N supply for the 12-y experimental period from 1998 to 2009. In contrast to earlier years, eCO 2 stimulated soil respiration twice as much at low than at high N supply from 2006 to 2009. In parallel, microbial C degradation genes were significantly boosted by eCO 2 at low but not high N supply. Further, incorporating those functional genes into a coupled C–N ecosystem model reduced model parameter uncertainty and improved the projections of the effects of different CO 2 and N levels on soil respiration. If our observed results generalize to other ecosystems, they imply widely positive effects of eCO 2 on soil respiration even in infertile systems.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2024

Neural simulation-based inference of the neutron star equation of state directly from telescope spectra

Neutron stars provide a unique opportunity to study strongly interacting matter under extreme density conditions. The intricacies of matter inside neutron stars and their equation of state are not directly visible, but determine bulk properties, such as mass and radius, which affect the star's thermal X-ray emissions. However, the telescope spectra of these emissions are also affected by the stellar distance, hydrogen column, and effective surface temperature, which are not always well-constrained. Uncertainties on these nuisance parameters must be accounted for when making a robust estimation of the equation of state. In this study, we develop a novel methodology that, for the first time, can infer the full posterior distribution of both the equation of state and nuisance parameters directly from telescope observations. This method relies on the use of neural likelihood estimation, in which normalizing flows use samples of simulated telescope data to learn the likelihood of the neutron star spectra as a function of these parameters, coupled with Hamiltonian Monte Carlo methods to efficiently sample from the corresponding posterior distribution. Our approach surpasses the accuracy of previous methods, improves the interpretability of the results by providing access to the full posterior distribution, and naturally scales to a growing number of neutron star observations expected in the coming years.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2020

Two-neutron knockout as a probe of the composition of states in Mg 22 , Al 23 , and Si 24

Simpson and Tostevin proposed that the width and shape of exclusive parallel momentum distributions of the A - 2 residue in direct two-nucleon knockout reactions carry a measurable sensitivity to the nucleon single-particle configurations and their couplings within the wave functions of exotic nuclei. We further report here on the first benchmarks and use of this new spectroscopic tool. Exclusive parallel momentum distributions for states in the neutron-deficient nuclei Mg 22 , Al 23 , and Si 24 populated in such direct two-neutron removal reactions were extracted and compared to predictions combining eikonal reaction theory and shell-model calculations. For the well-known Mg 22 and Al 23 nuclei, measurements and calculations were found to agree, supporting the dependence of the parallel momentum distribution width on the angular momentum composition of the shell-model two-neutron amplitudes. In Si 24 , a level at 3439(9) keV, of relevance for the important Al 23 ( p , γ ) Si 24 astrophysical reaction rate, was confirmed to be the 2 2 + state, whereas the 4 1 + state, expected to be strongly populated in two-neutron knockout, was not observed. This puzzle is resolved by theoretical considerations of the Thomas-Ehrman shift, which also indicates that a previously reported 3471-keV state in Si 24 is, in fact, the ( 0 2 + ) level with one of the largest experimental mirror-energy shifts ever observed.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2025

Measurement of multidifferential cross sections for dijet production in proton–proton collisions at $\sqrt{s}$ = 13 TeV

A measurement of the dijet production cross section is reported based on proton–proton collision data collected in 2016 at $\sqrt{s}$ = 13 TeV by the CMS experiment at the CERN LHC, corresponding to an integrated luminosity of up to 36.3 fb –1 . Jets are reconstructed with the anti-$k$ T algorithm for distance parameters of R = 0.4 and 0.8. Cross sections are measured double-differentially (2D) as a function of the largest absolute rapidity |y| max of the two jets with the highest transverse momenta $p$ T and their invariant mass $m$ 1,2 , and triple-differentially (3D) as a function of the rapidity separation $y$*, the total boost $y$ b , and either $m$ 1,2 or the average $p$ T of the two jets. The cross sections are unfolded to correct for detector effects and are compared with fixed-order calculations derived at next-to-next-to-leading order in perturbative quantum chromodynamics. The impact of the measurements on the parton distribution functions and the strong coupling constant at the mass of the Z boson is investigated, yielding a value of $α$ S ($m$ Z ) = 0.1179 ± 0.0019.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2026

Les Houches study on inclusive jet production at NNLO+NNLL

Jet production at the LHC is a powerful probe of QCD, making it ideal for precision tests and determinations of QCD parameters such as parton distribution functions and the strong coupling constant. To make the most of the abundant jet production data collected at the LHC, precise calculations are required. While state-of-the-art calculations reach next-to-next-to-leading order (NNLO) QCD accuracy, a critical assessment of the remaining uncertainties arising from non-perturbative effects and missing higher orders remains crucial for correctly interpreting comparisons between theory and data. Scale variation is nearly always used to determine effects from missing higher orders. In this article, we reassess this method in the context of inclusive jet production by performing NNLO QCD calculations supplemented by small-jet-radius resummation through next-to-next-to-leading-logarithmic accuracy (NNLL). We find that NNLL resummation can have an appreciable impact on the scale uncertainty for inclusive jet cross sections, and, for some scale choices, can lead to sizeable shifts of the central cross section. We conclude that scale variations in fixed-order and resummed calculations can drastically underestimate the impact of higher orders for commonly used jet radius parameters, and that missing higher-order estimates obtained via scale variations should be considered unreliable. Our findings add further evidence to the importance of going beyond scale variations in jet and jet substructure calculations.

Lee, Kyle↗
DOE OSTI2020

Transient voltage-reversal in transformers with multiple secondary coils

By using a transformer with multiple secondary coils, a single unipolar power source can drive multiple loads that have different steady-state operating-voltage requirements. We show that, during initial turn-on, a transient voltage that is opposite in sign to the operating voltage can be induced in one or more of the secondary coils. This is because the surging currents in the coils during turn-on produce a strong inductive interaction between all the coils. In a particular secondary coil, the voltage induced by a neighboring secondary can be larger, and opposite in sign to, the voltage directly induced by the primary coil. The effect is transient because, when the secondary circuits reach their steady-state operating currents, they no longer couple inductively to each other. We also show that, during the turn-on period, the voltage induced in a secondary coil can be significantly larger than its steady-state voltage. These transient effects are controlled by the values of the "coil-coupling" parameters, which are functions of the transformer geometry and of the magnetic permeability and electrical resistivity of the materials used. The results are derived from the circuit equations, and verified using PSpice simulations.

24 POWER TRANSMISSION AND DISTRIBUTION↗
DOE OSTI2021

Fully Implicit Monte Carlo (FIMC) (September 2019-September 2020 Progress Report)

This research is focused on applying the NLem method to the full thermal radiative transfer (TRT) equations in the context of a Monte Carlo solution strategy. A framework has been developed for obtaining a solution to the TRT equations using the nonlinear elimination method (NLem) method. Current efforts are focused of the development and verification of the required Monte Carlo algorithm, diffusion algorithm, and material energy solver. Once all three pieces have been verified, the algorithms will then be coupled into a fully functioning method for applying NLem to the TRT equations.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗