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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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49 records · Page 3

Fluctuation cepstral scanning transmission electron microscopy of mixed-phase amorphous materials

Four-dimensional scanning transmission electron microscopy (4D-STEM) is a versatile analytical tool for characterizing materials structural properties. However, extending such analysis to disordered materials is challenging, especially in technologically important samples with mixed ordered and disordered phases. Here, in this work, we present a new 4D-STEM method, called fluctuation cepstral STEM (FC-STEM), based on the fluctuation analysis of cepstral transform of diffraction patterns. The peaks in the associated transformation relate to inter-atomic distances in a thin sample. By varying the real-space range over which fluctuations are calculated, distinct ordered and disordered phases can be mapped in a diffractive image reconstruction. We demonstrate the principles of FC-STEM by characterizing a silicon anode, harvested from a cycled lithium-ion battery. A mixture of amorphous and nanocrystalline silicon, graphitic carbon, and electrolyte by-products is identified and mapped. Comparisons with conventional electron imaging and energy-dispersive X-ray spectroscopy show that FC-STEM is highly effective for the structure determination of mixed-phase amorphous materials.

36 MATERIALS SCIENCE↗

Evanescent operators in one-loop matching computations

Effective Field Theory calculations used in countless phenomenological analyses employ dimensional regularization, and at intermediate stages of computations, the operator bases extend beyond the four-dimensional ones. The extra pieces — the evanescent operators — can ultimately be removed with a suitable renormalization scheme, resulting in a finite shift of the physical operators. Modern Effective Field Theory matching techniques relying on the method of expansion by regions have to be extended to account for this. After illustrating the importance of these shifts in two specific examples, we compute the finite shifts required to remove all evanescent operators appearing in the one-loop matching of generic ultraviolet theories to the Standard Model Effective Field Theory and elucidate the formalism for generic Effective Field Theory calculations.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Cryogenic Vibrationally Resolved Photoelectron Spectroscopy of OH–(H2O): Confirmation of Multidimensional Franck-Condon Simulation Results for the Transition State of the OH + H2O Reaction

We present a transition state spectroscopic study of the OH + H2O reaction using the experimental technique of cryogenic Negative Ion Photoelectron Spectroscopy (NIPES). The recorded NIPE spectrum at 193 nm exhibits multiple vibrational progressions that include excitations to the shared H atom antisymmetric stretching mode with an interval of 0.32 eV as well as other progressions, mainly involving the H bending and O…O symmetric stretching modes. The Vertical Detachment Energy (VDE) was measured at 3.53 eV, whereas an upper limit for the Adiabatic Detachment Energy (ADE) was estimated at 2.90 eV. These values are in excellent agreement with the theoretically computed values of 3.51 eV and 2.83 eV respectively, obtained at the CCSD(T)/aug-cc-pV5Z level of theory. The recorded NIPE spectrum is in very good agreement when compared to the one recently reported from four-dimensional Franck-Condon simulations, in which a similar spectral profile was predicted. Besides observing the ground state, a charge-transfer excited state in the form of [OH–(H2O)+] is identified with a relative energy of 1.39 eV, well matching the previous prediction of 1.36 eV. This work was supported by U.S. Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences, and performed using EMSL, a national scientific user facility sponsored by DOE’s Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory, which is operated by Battelle Memorial Institute for the DOE. The theoretical calculations were conducted on EMSL’s “Cascade” Supercomputer. This research also used resources of the National Energy Research Scientific Computing Center, which is supported by the Office of Science of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231.

Cao, Wenjin↗

Correlative analysis of structure and chemistry of Li x FePO 4 platelets using 4D-STEM and X-ray ptychography

Lithium iron phosphate (Li x FePO 4 ), a cathode material used in rechargeable Li-ion batteries, phase separates upon de/lithiation under equilibrium. The interfacial structure and chemistry within these cathode materials affects Li-ion transport, and therefore battery performance. Here, correlative imaging of Li x FePO 4 was performed using four-dimensional scanning transmission electron microscopy (4D-STEM), scanning transmission X-ray microscopy (STXM), and X-ray ptychography in order to analyze the local structure and chemistry of the same particle set. Over 50,000 diffraction patterns from 10 particles provided measurements of both structure and chemistry at a nanoscale spatial resolution (16.6–49.5 nm) over wide (several micron) fields-of-view with statistical robustness. Li x FePO 4 particles at varying stages of delithiation were measured to examine the evolution of structure and chemistry as a function of delithiation. In lithiated and delithiated particles, local variations were observed in the degree of lithiation even while local lattice structures remained comparatively constant, and calculation of linear coefficients of chemical expansion suggest pinning of the lattice structures in these populations. Partially delithiated particles displayed broadly core–shell-like structures, however, with highly variable behavior both locally and per individual particle that exhibited distinctive intermediate regions at the interface between phases, and pockets within the lithiated core that correspond to FePO 4 in structure and chemistry. The results provide insight into the Li x FePO 4 system, subtleties in the scope and applicability of Vegard’s law (linear lattice parameter-composition behavior) under local versus global measurements, and demonstrate a powerful new combination of experimental and analytical modalities for bridging the crucial gap between local and statistical characterization.

25 ENERGY STORAGE↗

Probing for the Trace Estimation of a Permuted Matrix Inverse Corresponding to a Lattice Displacement

We report thatpProbing is a general technique that is used to reduce the variance of the Hutchinson stochastic estimator for the trace of the inverse of a large, sparse matrix A. The variance of the estimator is the sum of the squares of the off-diagonal elements of A -1 . Therefore, this technique computes probing vectors that when used in the estimator annihilate the largest off-diagonal elements. For matrices that display decay of the magnitude of |A$^{-1}_{ij}$| with the graph distance between nodes i and j, this is achieved through graph coloring of increasing powers A k . Equivalently, when a matrix stems from a lattice discretization, it is computationally beneficial to find a distance-k coloring of the lattice. Previously, a hierarchical coloring was proposed so that k can be increased at runtime as needed without discarding previous work. In this work, we study probing for the more general problem of computing the trace of a permutation of A -1 , say PA -1 . The motivation comes from lattice quantum chromodynamics (QCD), where we need to construct “disconnected diagrams” to extract flavor-separated generalized parton functions. In lattice QCD, where the matrix has a four-dimensional toroidal lattice structure, these nonlocal operators correspond to a PA -1 , where P is the permutation relating to some displacement $\vec{p}$ in one or more dimensions. We focus on a single dimension displacement (p), but our methods are general. We show that probing on A k or (PA) k does not annihilate the largest magnitude elements. To resolve this issue, our displacement-based probing works on PA k using a new coloring scheme that works directly on appropriately displaced neighborhoods on the lattice. We prove lower bounds on the number of colors needed and study the effect of this scheme on variance reduction, both theoretically and experimentally on a real-world lattice QCD calculation. We achieve orders of magnitude speedup over the unprobed or the naively probed methods.

97 MATHEMATICS AND COMPUTING↗

Mapping 1D Confined Electromagnetic Edge States in 2D Monolayer Semiconducting MoS 2 Using 4D-STEM

Here, four-dimensional (4D) scanning transmission electron microscopy is used to study the electric fields at the edges of 2D semiconducting monolayer MoS2. Sub-nanometer 1D features in the 2D electric field maps are observed at the outermost region along zigzag edges and also along nanowire MoS-terminated MoS 2 edges. Atomic-scale oscillations are detected in the magnitude of the 1D electromagnetic edge state, with spatial variations that depend on the specific periodic edge reconstructions. Electric field reconstructions, along with integrated differential phase contrast reconstructions, reveal the presence of low Z number atoms terminating many of the uniform edges, which are difficult to detect by annular dark field scanning transmission electron microscopy due to its limited dynamic range. Density functional theory calculations support the formation of periodic 1D edge states and also show that enhancement of the electric field magnitude can occur for some edge terminations. The experimentally observed electric fields at the edges are attributed to the absence of an opposing electric field from a nearest neighbor atom when the electron beam propagates through the 2D monolayer and interacts. These results show the potential of 4D-STEM to map the atomic scale structure and fluctuations of electric fields around edge atoms with different bonding states than bulk atoms in 2D materials, beyond conventional imaging.

2D materials↗

Unveiling Structural Heterogeneity and Imbalance of Gold Decahedral Nanoparticles using Four-dimensional Scanning Transmission Electron Microscopy

Multi-twinned structures have been observed in technologically important crystal systems, for example diamond cubic and face-centered cubic (FCC) lattices, that include materials such as diamond, silicon, a wide range of noble metals, and their nanoscale counterparts. Beyond atomic building blocks, the special arrangements also occur in the self-assembly of nanoparticles (NP) and μm-sized colloidal particles and occupy parts of their phase diagrams. Spanning a wide range of length scales, the universality of the structures arises when the systems attempt to achieve multitwinned structures by overcoming geometric misfits during minimizing surface energies with entirely {111} or close-packing facets. While it is fundamental to understand how strain is sustained upon twinned structures and symmetry breaking, the knowledge will be paramount in practical aspects such as guiding and controlling the thin film growth, anisotropic NP growth, and self-assembly of NPs. Au decahedral (Dh) NP, as the most prevalent multi-twinned model system, fits five tetrahedral motifs into a circle by sharing an axis resulting in a geometric misfit angle of 7.35°, or a disclination with power of -7.35°. Postulating how Au FCC lattice adopts the misfit, theoretical models have been developed to address the underlying lattice symmetry and inhomogeneous strain distribution separately. Yet, experimental reports regarding the former have been limited due to the relatively large X-ray beam sizes that do not fit the sizes of NPs. On the other hand, though the latter has been widely adapted in the thermodynamics of small (<10 nm) multi-twinned nanoparticles, previous literature has shown that, at edge length of 17 nm, the theory’s is invalidated by shear strain that is observed in a defect-free Au Dh NP by high-resolution transmission electron microscopy (HR-TEM) imaging. Though the advancement of aberrationcorrected scanning transmission electron microscopy (AC-STEM) imaging and ab initio calculation techniques brings new opportunities, along with challenges in complicated image analysis and limitation in particle size (usually below 10 nm), the gap between nanoscale and mesoscale has never been extended to gain insight from atomic system with straightforward interaction potentials.

4D-STEM↗

Conical-Domain Model for Estimating GPS Ionospheric Delays

The conical-domain model is a computational model, now undergoing development, for estimating ionospheric delays of Global Positioning System (GPS) signals. Relative to the standard ionospheric delay model described below, the conical-domain model offers improved accuracy. In the absence of selective availability, the ionosphere is the largest source of error for single-frequency users of GPS. Because ionospheric signal delays contribute to errors in GPS position and time measurements, satellite-based augmentation systems (SBASs) have been designed to estimate these delays and broadcast corrections. Several national and international SBASs are currently in various stages of development to enhance the integrity and accuracy of GPS measurements for airline navigation. In the Wide Area Augmentation System (WAAS) of the United States, slant ionospheric delay errors and confidence bounds are derived from estimates of vertical ionospheric delay modeled on a grid at regularly spaced intervals of latitude and longitude. The estimate of vertical delay at each ionospheric grid point (IGP) is calculated from a planar fit of neighboring slant delay measurements, projected to vertical using a standard, thin-shell model of the ionosphere. Interpolation on the WAAS grid enables estimation of the vertical delay at the ionospheric pierce point (IPP) corresponding to any arbitrary measurement of a user. (The IPP of a given user s measurement is the point where the GPS signal ray path intersects a reference ionospheric height.) The product of the interpolated value and the user s thin-shell obliquity factor provides an estimate of the user s ionospheric slant delay. Two types of error that restrict the accuracy of the thin-shell model are absent in the conical domain model: (1) error due to the implicit assumption that the electron density is independent of the azimuthal angle at the IPP and (2) error arising from the slant-to-vertical conversion. At low latitudes or at mid-latitudes under disturbed conditions, the accuracy of SBAS systems based upon the thin-shell model suffers due to the presence of complex ionospheric structure, high delay values, and large electron density gradients. Interpolation on the vertical delay grid serves as an additional source of delay error. The conical-domain model permits direct computation of the user s slant delay estimate without the intervening use of a vertical delay grid. The key is to restrict each fit of GPS measurements to a spatial domain encompassing signals from only one satellite. The conical domain model is so named because each fit involves a group of GPS receivers that all receive signals from the same GPS satellite (see figure); the receiver and satellite positions define a cone, the satellite position being the vertex. A user within a given cone evaluates the delay to the satellite directly, using (1) the IPP coordinates of the line of sight to the satellite and (2) broadcast fit parameters associated with the cone. The conical-domain model partly resembles the thin-shell model in that both models reduce an inherently four-dimensional problem to two dimensions. However, unlike the thin-shell model, the conical domain model does not involve any potentially erroneous simplifying assumptions about the structure of the ionosphere. In the conical domain model, the initially four-dimensional problem becomes truly two-dimensional in the sense that once a satellite location has been specified, any signal path emanating from a satellite can be identified by only two coordinates; for example, the IPP coordinates. As a consequence, a user s slant-delay estimate converges to the correct value in the limit that the receivers converge to the user s location (or, equivalently, in the limit that the measurement IPPs converge to the user s IPP).

Sparks, Lawrence↗

Effective entropy of quantum fields coupled with gravity

Entanglement entropy, or von Neumann entropy, quantifies the amount of uncertainty of a quantum state. For quantum fields in curved space, entanglement entropy of the quantum field theory degrees of freedom is well-defined for a fixed background geometry. In this paper, we propose a generalization of the quantum field theory entanglement entropy by including dynamical gravity. The generalized quantity named effective entropy, and its Renyi entropy generalizations, are defined by analytic continuation of a replica calculation. The replicated theory is defined as a gravitational path integral with multiple copies of the original boundary conditions, with a co-dimension-2 brane at the boundary of region we are studying. We discuss different approaches to define the region in a gauge invariant way, and show that the effective entropy satisfies the quantum extremal surface formula. When the quantum fields carry a significant amount of entanglement, the quantum extremal surface can have a topology transition, after which an entanglement island region appears. Our result generalizes the Hubeny-Rangamani-Takayanagi formula of holographic entropy (with quantum corrections) to general geometries without asymptotic AdS boundary, and provides a more solid framework for addressing problems such as the Page curve of evaporating black holes in asymptotic flat spacetime. We apply the formula to two example systems, a closed two-dimensional universe and a four-dimensional maximally extended Schwarzchild black hole. We discuss the analog of the effective entropy in random tensor network models, which provides more concrete understanding of quantum information properties in general dynamical geometries. We show that, in absence of a large boundary like in AdS space case, it is essential to introduce ancilla that couples to the original system, in order for correctly characterizing quantum states and correlation functions in the random tensor network. Using the superdensity operator formalism, we study the system with ancilla and show how quantum information in the entanglement island can be reconstructed in a state-dependent and observer-dependent map. We study the closed universe (without spatial boundary) case and discuss how it is related to open universe.

79 ASTRONOMY AND ASTROPHYSICS↗

De Sitter decays to infinity

Bubbles of nothing are a class of vacuum decay processes present in some theories with compactified extra dimensions. We investigate the existence and properties of bubbles of nothing in models where the scalar pseudomoduli controlling the size of the extra dimensions are stabilized at positive vacuum energy, which is a necessary feature of any realistic model. We map the construction of bubbles of nothing to a four-dimensional Coleman-De Luccia problem and establish necessary conditions on the asymptotic behavior of the scalar potential for the existence of suitable solutions. We perform detailed analyses in the context of five-dimensional theories with metastable dS 4 x S 1 vacua, using analytic approximations and numerical methods to calculate the decay rate. We find that bubbles of nothing sometimes exist in potentials with no ordinary Coleman-De Luccia decay process, and that in the examples we study, when both processes exist, the bubble of nothing decay rate is typically faster. Our methods can be generalized to other stabilizing potentials and internal manifolds.

classical theories of gravity↗

Estimating biofuel contaminant concentration from 4D ERT with mixing models

Here, we present the results of a lab-scaled feasibility study to assess the performance of electrical resistivity tomography for detection, characterization, and monitoring of fuel grade ethanol releases to the subsurface. Further, we attempt to determine the concentration distribution of the ethanol from the electrical resistivity tomography data using mixing-models. Ethanol is a renewable fuel source as well as an oxygenate fuel additive currently used to replace the known carcinogen methyl tert-butyl ether; however, ethanol is preferentially biodegraded and a cosolvent. When introduced to areas previously impacted by nonethanol-based fuels, it will facilitate the persistence of carcinogenic fuel compounds like benzene and ethylbenzene, as well as remobilize them to the ground water. These compounds would otherwise be retained in the soil column undergoing active or passive remediation processes such as soil vapor extraction or natural attenuation. Here, we introduce ethanol to a saturated Ottawa sand in a tank instrumented for four-dimensional geoelectrical measurements. Forward model results suggest pure phase ethanol released into a water saturated silica sand should present a detectable target for electrical resistivity tomography relative to a saturated silica sand only. We observe the introduction of ethanol to the closed hydraulic system and subsequent migration over the duration of the experiment. One-dimensional and three–dimensional temporal data are assessed for the detection, characterization, and monitoring of the ethanol release. Results suggest one-dimensional geoelectrical measurements may be useful for monitoring a release, while three-dimensional geoelectrical field imaging would be useful to characterize, monitor, and design effective remediation approaches for an ethanol release, assuming field conditions do not preclude the application of geoelectrical methods. We then attempt to use predictive mixing models to calculate the distribution of ethanol concentration within the measurement domain. For this study we examine four different models: a nested parallel mixing model, a nested cubic mixing model, the complex refractive index model (CRIM), and the Lichtenecker-Rother (L-R) model. The L-R model, modified to include an electrical formation factor geometry term, provided the best agreement with expected EtOH concentrations.

09 BIOMASS FUELS↗

Robust Tensor Hypercontraction of the Particle–Particle Ladder Term in Equation-of-Motion Coupled Cluster Theory

One method of representing a high-rank tensor as a (hyper-)product of lower-rank tensors is the tensor hypercontraction (THC) method of Hohenstein et al. This strategy has been found to be useful for reducing the polynomial scaling of coupled-cluster methods by representation of a four-dimensional tensor of electron-repulsion integrals in terms of five two-dimensional matrices. Pierce et al. have already shown that the application of a robust form of THC to the particle–particle ladder (PPL) term reduces the cost of this term in couple-cluster singles and doubles (CCSD) from O(N 6 ) to O(N 5 ) with negligible errors in energy with respect to the density-fitted variant. In this work, we have implemented the least-squares variant of THC (LS-THC) which does not require a nonlinear tensor factorization, including the robust form (R-LS-THC), for the calculation of the excitation and electron attachment energies using equation-of-motion coupled cluster methods EOMEE-CCSD and EOMEA-CCSD, respectively. We have benchmarked the effect of the R-LS-THC-PPL approximation on excitation energies using the comprehensive QUEST database and the accuracy of electron attachment energies using the NAB22 database. Here, we find that errors on the order of 1 meV are achievable with a reduction in total calculation time of approximately 5x.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Nonrenormalization and Operator Mixing via On-Shell Methods

Using on-shell methods, we present a new perturbative nonrenormalization theorem for operator mixing in massless four-dimensional quantum field theories. By examining how unitarity cuts of form factors encode anomalous dimensions, we show that longer operators are often restricted from renormalizing shorter operators at the first order where Feynman diagrams exist. The theorem applies quite generally and depends only on the field content of the operators involved. We apply our theorem to operators of dimension five through seven in the standard model effective field theory, including examples of nontrivial zeros in the anomalous-dimension matrix at one through four loops. The zeros at two and higher loops go beyond those previously explained using helicity selection rules. We also include explicit sample calculations at two loops.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗