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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
All sourcesNASA NTRSDOE OSTI
DOE OSTI2015

Signature of a polyamorphic transition in the THz spectrum of vitreous GeO 2

The THz spectrum of density fluctuations, S(Q, ω), of vitreous GeO 2 at ambient temperature was measured by inelastic x-ray scattering from ambient pressure up to pressures well beyond that of the known α-quartz to rutile polyamorphic (PA) transition. We observe significant differences in the spectral shape measured below and above the PA transition, in particular, in the 30–80 meV range. Guided by first-principle lattice dynamics calculations, we interpret the changes in the phonon dispersion as the evolution from a quartz-like to a rutile-like coordination. Notably, such a crossover is accompanied by a cusp-like behavior in the pressure dependence of the elastic response of the system. Altogether, the presented results highlight the complex fingerprint of PA phenomena on the high-frequency phonon dispersion.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2019

Site-averaged kinetics for catalysts on amorphous supports: an importance learning algorithm

Ab initio calculations have greatly advanced our understanding of homogeneous catalysts and crystalline heterogeneous catalysts. In contrast, amorphous heterogeneous catalysts remain poorly understood. The principal difficulties include (i) the nature of the disorder is quenched and unknown; (ii) each active site has a different local environment and activity; (iii) active sites are rare, often less than ~20% of potential sites, depending on the catalyst and its preparation method. Few (if any) studies of amorphous heterogeneous catalysts have ever attempted to compute site-averaged kinetics, because the exponential dependence on variable activation energy requires an intractable number of ab initio calculations to converge. We present a new algorithm using machine learning techniques (metric learning kernel regression) and importance sampling to efficiently learn the distribution of activation energies. We demonstrate the algorithm by computing the site-averaged activity for a model amorphous catalyst with quenched disorder.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Grafting metal complexes onto amorphous supports: from elementary steps to catalyst site populations via kernel regression

Ab initio computational studies have made tremendous progress in describing the behavior of molecular (homogeneous) catalysts and crystalline versions of heterogeneous catalysts, but not for amorphous heterogeneous catalysts. Even widely used industrial amorphous catalysts like atomically dispersed Cr on silica remain poorly understood and largely intractable to computational investigation. The central problems are that (i) the amorphous support presents an unknown quenched disordered structure, (ii) metal atoms attach to various surface grafting sites with different rates, and (iii) the resulting grafted sites have different activation and catalytic reaction kinetics. This study combines kernel regression and importance sampling techniques to efficiently model grafting of metal ions onto a non-uniform ensemble of support environments. Our analysis uses a simple model of the quenched disordered support environment, grafting chemistry, and catalytic activity of the resulting grafted sites.

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

Population balance models for polymer upcycling: signatures of the mechanism in the molecular weight evolution

Chemical and catalytic upcycling processes could help realize a circular plastics economy, but current models for testing mechanistic hypotheses and designing catalysts remain primitive. This work shows how proposed catalytic mechanisms can be incorporated into population balance models to predict the time evolution of molecular weight distributions. We develop models for homogeneous and heterogeneous catalysts, including catalysts that cut at chain ends and catalysts that cut at random locations. For heterogeneous catalysts, we illustrate the effect of adsorption constants that depend on polymer chain length. Here, we discuss ongoing efforts and challenges in measuring and modeling the time evolving molecular weight distributions in polymer upcycling processes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

The Carnegie Supernova Project I: Spectroscopic analysis of stripped-envelope supernovae

An analysis leveraging 170 optical spectra of 35 stripped-envelope (SE) core-collapse supernovae (SNe) observed by the Carnegie Supernova Project I and published in a companion paper is presented. Mean template spectra were constructed for the SNe IIb, Ib, and Ic subtypes, and parent ions associated with designated spectral features are identified with the aid of the spectral synthesis code SYNAPPS. Our modeled mean spectra suggest the ~6150 Å feature in SNe IIb may have an underlying contribution due to silicon, while the same feature in some SNe Ib may have an underlying contribution due to hydrogen. Standard spectral line diagnostics consisting of pseudo-equivalent widths (pEWs) and blue-shifted Doppler velocity were measured for each of the spectral features. Correlation matrices and rolling mean values of both spectral diagnostics were constructed. A principle component analysis (PCA) was applied to various wavelength ranges of the entire dataset and suggests clear separation among the different SE SN subtypes, which follows from trends previously identified in the literature. In addition, our findings reveal the presence of two SNe IIb subtypes, a select number of SNe Ib displaying signatures of weak, high-velocity hydrogen, and a single SN Ic with evidence of weak helium features. Our PCA results can be leveraged to obtain robust subtyping of SE SNe based on a single spectrum taken during the so-called photospheric phase, separating SNe IIb from SNe Ib with ~80% completion.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2025

Euclid I. Overview of the Euclid mission

The current standard model of cosmology successfully describes a variety of measurements, but the nature of its main ingredients, dark matter and dark energy, remains unknown. Euclid is a medium-class mission in the Cosmic Vision 2015–2025 programme of the European Space Agency (ESA) that will provide high-resolution optical imaging, as well as near-infrared imaging and spectroscopy, over about 14 000 deg 2 of extragalactic sky. In addition to accurate weak lensing and clustering measurements that probe structure formation over half of the age of the Universe, its primary probes for cosmology, these exquisite data will enable a wide range of science. This paper provides a high-level overview of the mission, summarising the survey characteristics, the various data-processing steps, and data products. We also highlight the main science objectives and expected performance.

cosmology↗
DOE OSTI2011

Photoinduced variable stiffness of spiropyran-based composites

A quantitative demonstration of reversible stiffness upon appropriate light stimulus in a spiropyran-polymeric composite is presented. The polymeric films containing 3% wt. of the photochromic spiropyran were irradiated with alternating ultraviolet and visible light and the storage modulus was measured. A reversible change in modulus of about 7% was observed. The modulus change was attributed to an interaction of the polar merocyanine with the polymeric chains and/or to a variation of effective free volume induced by merocyanine aggregates formed in the polymer upon ultraviolet irradiation. The effect is fully reversed when the merocyanine isomers turn back to the spiropyran state after visible irradiation.

36 MATERIALS SCIENCE↗
DOE OSTI2013

Analysis of the AlGaN/GaN vertical bulk current on Si, sapphire, and free-standing GaN substrates

The vertical bulk (drain-bulk) current (I{sub db}) properties of analogous AlGaN/GaN hetero-structures molecular beam epitaxially grown on silicon, sapphire, and free-standing GaN (FS-GaN) have been evaluated in this paper. The experimental I{sub db} (25-300 Degree-Sign C) have been well reproduced with physical models based on a combination of Poole-Frenkel (trap assisted) and hopping (resistive) conduction mechanisms. The thermal activation energies (E{sub a}), the (soft or destructive) vertical breakdown voltage (V{sub B}), and the effect of inverting the drain-bulk polarity have also been comparatively investigated. GaN-on-FS-GaN appears to adhere to the resistive mechanism (E{sub a} = 0.35 eV at T = 25-300 Degree-Sign C; V{sub B} = 840 V), GaN-on-sapphire follows the trap assisted mechanism (E{sub a} = 2.5 eV at T > 265 Degree-Sign C; V{sub B} > 1100 V), and the GaN-on-Si is well reproduced with a combination of the two mechanisms (E{sub a} = 0.35 eV at T > 150 Degree-Sign C; V{sub B} = 420 V). Finally, the relationship between the vertical bulk current and the lateral AlGaN/GaN transistor leakage current is explored.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2013

Density functional theory study of the interaction of vinyl radical, ethyne, and ethene with benzene, aimed to define an affordable computational level to investigate stability trends in large van der Waals complexes

Our purpose is to identify a computational level sufficiently dependable and affordable to assess trends in the interaction of a variety of radical or closed shell unsaturated hydro-carbons A adsorbed on soot platelet models B. These systems, of environmental interest, would unavoidably have rather large sizes, thus prompting to explore in this paper the performances of relatively low-level computational methods and compare them with higher-level reference results. To this end, the interaction of three complexes between non-polar species, vinyl radical, ethyne, or ethene (A) with benzene (B) is studied, since these species, involved themselves in growth processes of polycyclic aromatic hydrocarbons (PAHs) and soot particles, are small enough to allow high-level reference calculations of the interaction energy ΔE{sub AB}. Counterpoise-corrected interaction energies ΔE{sub AB} are used at all stages. (1) Density Functional Theory (DFT) unconstrained optimizations of the A−B complexes are carried out, using the B3LYP-D, ωB97X-D, and M06-2X functionals, with six basis sets: 6-31G(d), 6-311 (2d,p), and 6-311++G(3df,3pd); aug-cc-pVDZ and aug-cc-pVTZ; N07T. (2) Then, unconstrained optimizations by Møller-Plesset second order Perturbation Theory (MP2), with each basis set, allow subsequent single point Coupled Cluster Singles Doubles and perturbative estimate of the Triples energy computations with the same basis sets [CCSD(T)//MP2]. (3) Based on an additivity assumption of (i) the estimated MP2 energy at the complete basis set limit [E{sub MP2/CBS}] and (ii) the higher-order correlation energy effects in passing from MP2 to CCSD(T) at the aug-cc-pVTZ basis set, ΔE{sub CC-MP}, a CCSD(T)/CBS estimate is obtained and taken as a computational energy reference. At DFT, variations in ΔE{sub AB} with basis set are not large for the title molecules, and the three functionals perform rather satisfactorily even with rather small basis sets [6-31G(d) and N07T], exhibiting deviation from the computational reference of less than 1 kcal mol{sup −1}. The zero-point vibrational energy corrected estimates Δ(E{sub AB}+ZPE), obtained with the three functionals and the 6-31G(d) and N07T basis sets, are compared with experimental D{sub 0} measures, when available. In particular, this comparison is finally extended to the naphthalene and coronene dimers and to three π−π associations of different PAHs (R, made by 10, 16, or 24 C atoms) and P (80 C atoms)

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2013

A quantum Cherry theorem for perturbations of the plane rotator

We consider on L{sup 2}(T{sup 2}) the Schrödinger operator family L{sub ε}:ε∈R with domain and action defined as D(L{sub ε})=H{sup 2}(T{sup 2}), L{sub ε}u=−(1/2)ℏ{sup 2}(α{sub 1}∂{sub φ{sub 1}{sup 2}}+α{sub 2}∂{sub φ{sub 2}{sup 2}})u−iℏ(γ{sub 1}∂{sub φ{sub 1}}+γ{sub 2}∂{sub φ{sub 2}})u+εVu. Here ε∈R, α= (α{sub 1}, α{sub 2}), γ= (γ{sub 1}, γ{sub 2}) are vectors of complex non-real frequencies, and V a pseudodifferential operator of order zero. L{sub ε} represents the Weyl quantization of the Hamiltonian family L{sub ε}(ξ,x)=(1/2)(α{sub 1}ξ{sub 1}{sup 2}+α{sub 2}ξ{sub 2}{sup 2})+γ{sub 1}ξ{sub 1}+γ{sub 2}ξ{sub 2}+εV(ξ,x) defined on the phase space R{sup 2}×T{sup 2}, where V(ξ,x)∈C{sup 2}(R{sup 2}×T{sup 2};R). We prove the uniform convergence with respect to ℏ∈[0, 1] of the quantum normal form, which reduces to the classical one for ℏ= 0. This result simultaneously entails an exact quantization formula for the quantum spectrum as well as a convergence criterion for the classical Birkhoff normal form generalizing a well known theorem of Cherry.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2014

Accurate molecular structures and infrared spectra of trans-2,3-dideuterooxirane, methyloxirane, and trans-2,3-dimethyloxirane

Oxirane derivatives are the most used benchmarks for chiroptical spectroscopies in view of their small size and relative rigidity. The molecular structure, vibrational harmonic and anharmonic frequencies, and infrared intensities of the ground electronic states are analyzed in this paper. Equilibrium structure and harmonic force fields have been evaluated by means of high-level quantum-chemical calculations at the coupled-cluster level including single and double excitations together with a perturbative treatment of triples (CCSD(T)). Extrapolation to the complete basis-set limit as well as core-correlation effects have also been taken into account. Anharmonic contributions have been computed at the CCSD(T)/cc-pVTZ level for trans-2,3-dideuterooxirane. These data can serve as references to evaluate the accuracy of less expensive computational approaches rooted in the density functional theory (DFT). The latter have been used within hybrid CC/DFT approaches, which have been applied to simulate fully anharmonic infrared (IR) spectra. Finally, the best theoretical estimates of the equilibrium structures and vibrational wavenumbers are compared to the most accurate experimental data and show in all cases very good agreement, i.e., within 0.001 Å, 0.1 deg, 10 cm{sup −1}, and 0.5 km mol{sup −1}, for bond lengths, angles, wavenumbers, and IR intensities, respectively.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

A general time-dependent route to Resonance-Raman spectroscopy including Franck-Condon, Herzberg-Teller and Duschinsky effects

We present a new formulation of the time-dependent theory of Resonance-Raman spectroscopy (TD-RR). Particular attention has been devoted to the generality of the framework and to the possibility of including different effects (Duschinsky mixing, Herzberg-Teller contributions). Furthermore, the effects of different harmonic models for the intermediate electronic state are also investigated. Thanks to the implementation of the TD-RR procedure within a general-purpose quantum-chemistry program, both solvation and leading anharmonicity effects have been included in an effective way. The reliability and stability of our TD-RR implementation are validated against our previously proposed and well-tested time-independent procedure. Practical applications are illustrated with some closed- and open-shell medium-size molecules (anthracene, phenoxyl radical, benzyl radical) and the simulated spectra are compared to the experimental results. More complex and larger systems, not limited to organic compounds, can be also studied, as shown for the case of Tris(bipyridine)ruthenium(II) chloride.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗