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DOE OSTI2011

Search of anomalous $Wtb$ couplins in single top quark prodution at D0

The large mass of the top quark, close to the electroweak symmetry-breaking scale, makes it a good candidate for probing physics beyond the Standard Model, including possible anomalous couplings. D0 has made measurements of single top quark production using 5.4 fb{sup -1} of integrated luminosity. We examine the data to study the Lorentz structure of the Wtb coupling. We find that the data prefer the left-handed vector coupling and set upper limits on the anomalous couplings. In 2009, the electroweak single top quark production was observed by the D0 and CDF collaborations. Electroweak production of top quarks at the Tevatron proceeds mainly via the decay of a time-like virtual W boson accompanied by a bottom quark in the s-channel (tb = t{bar b} + {bar t}b), or via the exchange of a space-like virtual W boson between a light quark and a bottom quark in the t-channel (tqb = tq{bar b} + {bar t}qb, where q refers to the light quark). For a top quark mass of 172.5 GeV, The Standard Model (SM) prediction of single top production rate at next-to-leading order with soft-gluon contributions at next-to-next-to-leading order are 1.04 {+-} 0.04 pb (s-channel) and 2.26 {+-} 0.12 pb (t-channel). The large mass of the top quark implies that it has large couplings to the electroweak symmetry breaking sector of the SM and may have non-standard interactions with the weak gauge bosons. Single top quark production provides a unique probe to study the interactions of the top quark with the W boson.

43 PARTICLE ACCELERATORS↗

DOE OSTI2019

Coexistence of Magnetic Orders in Two-Dimensional Magnet CrI3

The magnetic properties in two-dimensional van der Waals materials depend sensitively on structure. CrI 3 , as an example, has been recently demonstrated to exhibit distinct magnetic properties depending on the layer thickness and stacking order. Bulk CrI 3 is ferromagnetic (FM) with a Curie temperature of 61 K and a rhombohedral layer stacking, whereas few-layer CrI 3 has a layered antiferromagnetic (AFM) phase with a lower ordering temperature of 45 K and a monoclinic stacking. In this work, we use cryogenic magnetic force microscopy to investigate CrI 3 flakes in the intermediate thickness range (25–200 nm) and find that the two types of magnetic orders, hence the stacking orders, can coexist in the same flake with a layer of ~13 nm at each surface being in the layered AFM phase similar to few-layer CrI 3 and the rest in the bulk FM phase. The switching of the bulk moment proceeds through a remnant state with nearly compensated magnetic moment along the c-axis, indicating formation of c-axis domains allowed by a weak interlayer coupling strength in the rhombohedral phase. Our research provides a comprehensive picture on the magnetism in CrI 3 and point to the possibility of engineering magnetic heterostructures within the same material.

2D magnets↗

DOE OSTI2014

A Unified Picture of Adsorption on Transition Metals through Different Atoms

A key issue in catalyst design is understanding how adsorption energies of surface intermediates vary across both different surfaces and various types of adsorbing atoms. In this work, we examine trends in adsorption energies of a wide variety of adsorbates that attach to transition metal surfaces through different atoms (H, C, N, O, F, S, etc.). All adsorption energies, as calculated by density functional theory, have nearly identical dependence on the metal bands (the d-band center and the number of p electrons) and the adsorbates’ highest occupied molecular orbital (HOMO) energies. However, the dependence on the adsorbate-surface coupling and the d-band filling varies with the energy of the HOMO. Adsorbates with low HOMOs experience a higher level of Pauli repulsion than those with higher HOMOs. This leads to a classification of adsorbates into two groups, where adsorption energies in each group correlate. Even across the groups, adsorbates with similar HOMO energies are likely to have correlated adsorption energies.

Environmental Molecular Sciences Laboratory↗

DOE OSTI2021

Helical versus collinear antiferromagnetic order tuned by magnetic anisotropy in polar and chiral (Ni,Mn) 3 TeO 6

In this work, polar and chiral Ni 3 TeO 6 was found to exhibit a colossal magnetoelectric (ME) effect associated with collinear antiferromagnetic order. We have investigated the evolution of its magnetic state with the substitution of the Ni 2+ spins by isotropic Mn 2+ spins, namely (Ni, Mn) 3 TeO 6 (NMTO). The ground state of NMTO maintains an Ising nature, but a new phase with XY-type magnetic anisotropy is discovered at an intermediate temperature range. Neutron powder diffraction experiments reveal that (1) Mn ions tend to occupy a specific transition-metal site, consistent with the first-principle calculation, and (2) the intermediate phase is an incommensurate (IC) helical magnetic state propagating along the $\textit{c}$ axis with $\vec q_{\text{IC}}$ = (0, 0, 1.5 ± δ). We also found that the balance between these two magnetic states can be readily manipulated with magnetic fields, which results in significant ME effects. This selective site occupancy of NMTO allows for a unique competition between collinear and helical magnetic structures with minimal chemical disorder. Thus, NMTO serves as a model system to study site-specific chemical control of noncollinear magnetism and ME coupling.

36 MATERIALS SCIENCE↗

DOE OSTI2018

Optimizing Tensor Contractions in CCSD(T) for Efficient Execution on GPUs

Tensor contractions are higher dimensional analogs of matrix multiplications, used in many computational contexts such as high order models in quantum chemistry, deep learning, nite element methods etc. In contrast to the wide availability of high-performance libraries for matrix multiplication on GPUs, the same is not true for tensor contractions. In this paper, we address the optimization of a set of symmetrized tensor contractions that form the computational bottleneck in the CCSD(T) coupled-cluster method in computational chemistry suites like NWChem. Some of the challenges in optimizing tensor contractions that arise in practice from the variety of dimensionalities and shapes for tensors include effective mapping of the high-dimensional iteration space to threads, choice of data buffering in shared-memory and registers, and tile sizes for multi-level tiling. Furthermore, in the case of symmetrized tensor contractions in CCSD(T), it is also a challenge to fuse contractions to reduce data movement cost by exploiting reuse of intermediate tensors. In this paper, we developed an efficient GPU implementation of the tensor contractions in CCSD(T) using shared-memory buffering, register tiling, loop fusion and register transpose. Experimental results demonstrate significant improvement over the current state-of-the-art.

Kim, Jinsung↗

DOE OSTI2021

Development of an in situ dual-channel thermal desorption gas chromatography instrument for consistent quantification of volatile, intermediate-volatility and semivolatile organic compounds

Abstract. Aerosols are a source of great uncertainty in radiative forcing predictions and have poorly understood health impacts. Most aerosol mass is formed in the atmosphere from reactive gas-phase organic precursors, forming secondary organic aerosol (SOA). Semivolatile organic compounds (SVOCs) (effective saturation concentration, C*, of 10−1–103 µg m−3) comprise a large fraction of organic aerosol, while intermediate-volatility organic compounds (IVOCs) (C* of 103–106 µg m−3) and volatile organic compounds (VOCs) (C* ≥ 106 µg m−3) are gas-phase precursors to SOA and ozone. The Comprehensive Thermal Desorption Aerosol Gas Chromatograph (cTAG) is the first single instrument simultaneously quantitative for a broad range of compound-specific VOCs, IVOCs and SVOCs. cTAG is a two-channel instrument which measures concentrations of C5–C16 alkane-equivalent-volatility VOCs and IVOCs on one channel and C14–C32 SVOCs on the other coupled to a single high-resolution time-of-flight mass spectrometer, achieving consistent quantification across 15 orders of magnitude of vapor pressure. cTAG obtains concentrations hourly and gas–particle partitioning for SVOCs every other hour, enabling observation of the evolution of these species through oxidation and partitioning into the particle phase. Online derivatization for the SVOC channel enables detection of more polar and oxidized species. In this work we present design details and data evaluating key parameters of instrument performance such as I/VOC collector design optimization, linearity and reproducibility of calibration curves obtained using a custom liquid evaporation system for I/VOCs and the effect of an ozone removal filter on instrument performance. Example timelines of precursors with secondary products are shown, and analysis of a subset of compounds detectable by cTAG demonstrates some of the analytical possibilities with this instrument.

54 ENVIRONMENTAL SCIENCES↗

NASA NTRS1981

Nucleocosmochronology

Nucleocosmochronology is analyzed on the basis of elemental isotopic abundances of radionuclides. The production and depletion mechanisms for the cosmological chronometers are investigated and model-independent theories are reviewed. Emphasis is given to the significance of the mean age of the elements and the time resolution of the last nucleosynthetic events contributing to the solar system, and it is shown how the intermediate-lived chronometers may give information on the time dependence shape of the production function. Anomalous nucleocosmochronology is investigated and galactic and cosmological constraints are described in terms of time scales for the mean age of elements and galaxies and the age of the universe. Data resulting from both model-independent and dependent analyses are compared. Results based on the mean age for the r-process elements suggest a lower limit to the age of the galaxy and the universe. It is concluded that nucleocosmochronology, when coupled with other independent determinations for the age of the universe, defines a concordant universe age of 13.5-15.5 billion years. The shape of the production function is not well determined because of the uncertainties in the xenon data.

Symbalisty, E. M. D.↗

DOE OSTI2016

Innovative Waste Packaging and Associated Venting/Hydrogen Management - 16594

The original strategy for managing intermediate level waste (ILW) was developed in the 1980s by the UK Nuclear Industry Radioactive Waste Executive (NIREX), which is now the Radioactive Waste Management Limited (RWM), a wholly owned subsidiary of the Nuclear Decommissioning Authority (NDA). The strategy involved retrieving ILW, sorting and encapsulating it in cement based grout within thin walled stainless steel containers. The containers would then be transferred to a large purpose-built shielded ILW store on site, where they would be stored until the planned final deep geological disposal facility becomes available. In recognition of the high up-front costs of such a strategy, which requires remote facilities for the encapsulation and storage, and coupled with the long programme duration for the design, construction and commissioning of these facilities, waste management organisations responsible for managing the clean-up of legacy facilities within the UK have, in recent years, sought innovative solutions which could potentially both accelerate clean-up and hazard reduction on sites, and with a lower overall programme lifecycle cost. Many of the recent innovative solutions are focused around a new family of packaging designs known as robust shielded containers (RSCs). These are self-shielded containers manufactured from materials such as ductile cast iron or fabricated steel. These containers offer the potential to package wastes for disposal without encapsulation and avoid the need for a highly engineered remote handled shielded store for interim storage. The paper provides a high level overview of the generic concepts of RSCs developed by Croft and focuses on the specific challenges of wasteform evolution on waste package integrity and performance. In particular, the integrity and performance of the filtered vent system required to manage internal pressurisation and to ensure sufficient venting capacity of hydrogen and other evolved gases. The paper summarises the analysis by ARUP undertaken to substantiate the RSC integrity under detonation/deflagration explosion loadings arising from hydrogen accumulation. Analyses of the structural response of the filter assembly were undertaken for both detonation and deflagration explosion scenarios, with the loadings applied to the filter housing rim and to the filter vent cover. The paper also presents evidence of the mechanical performance of the filter medium in terms of pressure transients during deflagration events and the degree to which filtration efficiency is maintained. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

DOE OSTI2022

Optimizing feed modulation for coupled methane and NO x conversion over Pd-Pt/Mn 0.5 Fe 2.5 O 4 /Al 2 O 3 monolith catalyst

Here the impacts of feed modulation (frequency, amplitude) and catalyst design (composition and architecture) parameters are reported for the conversion of methane and NO x over a dual-layer Pt+Pd/Al 2 O 3 + Mn 0.5 Fe 2.5 O 4 /Al 2 O 3 monolith. CH 4 and NO x conversion data show that the dual-layer catalyst outperforms single-layer samples having the same catalyst loadings, with and without spinel. Close proximity of the PGM and MFO functions in the mixed-layer catalyst lowers the CH 4 conversion at high temperature while separating the PGM and spinel layers with an intermediate Al 2 O 3 layer does not. Methane conversion enhancement is linked to its nonmonotonic dependence on O 2 . The performance gains are tied to a transient activity spike that occurs during the lean-to-rich feed transition when water is present in the feed. The transient spike is attributed to the removal of CO and H 2 products via reactions with stored O 2 in the spinel, eliminating inhibition of methane steam reforming.

03 NATURAL GAS↗

DOE OSTI2022

Atomically Thin, Ionic–Covalent Organic Nanosheets for Stable, High–Performance Carbon Dioxide Electroreduction

The incorporation of charged functional groups is effective to modulate the activity of molecular complexes for the CO 2 reduction reaction (CO 2 RR), yet long-term heterogeneous electrolysis is often hampered by catalyst leaching. Herein, an electrocatalyst of atomically thin, cobalt-porphyrin-based, ionic–covalent organic nanosheets (CoTAP-iCONs) is synthesized via a post-synthetic modification strategy for high-performance CO 2 -to-CO conversion. The cationic quaternary ammonium groups not only enable the formation of monolayer nanosheets due to steric hindrance and electrostatic repulsion, but also facilitate the formation of a *COOH intermediate, as suggested by theoretical calculations. Consequently, CoTAP-iCONs exhibit higher CO 2 RR activity than other cobalt-porphyrin-based structures: an 870% and 480% improvement of CO current densities compared to the monomer and neutral nanosheets, respectively. Additionally, the iCONs structure can accommodate the cationic moieties. In a flow cell, CoTAP-iCONs attain a very small onset overpotential of 40 mV and a stable total current density of 212 mA cm –2 with CO Faradaic efficiency of >95% at –0.6 V for 11 h. Further coupling the flow electrolyzer with commercial solar cells yields a solar-to-CO conversion efficiency of 13.89%. Finally, this work indicates that atom-thin, ionic nanosheets represent a promising structure for achieving both tailored activity and high stability.

36 MATERIALS SCIENCE↗

DOE OSTI2019

Coupled CFD and chemical-kinetics simulations of cellulosic-biomass enzymatic hydrolysis: Mathematical-model development and validation

Computational simulations of cellulosic-biomass enzymatic hydrolysis using a computational-fluid-dynamics (CFD) model coupled to a chemical-kinetics model are presented in this work. A time-step sub-cycling strategy was used to circumvent large disparities in time scales with respect to transport physics and chemical kinetics. The unknown reaction and transport parameters in the mathematical model were first fit to two canonical experiments: a well-mixed case that was limited by reaction kinetics and a settled-solids case that was limited by transport. Here, the model was then validated against a benchtop experiment for an intermediate-mixing scenario, for which simulation results were in reasonable agreement with experimentally measured cellulose conversions. Settling of cellulose particles and diffusion of enzymes determine overall conversion rates for lower mixing rates, while reaction rates dominate conversion at higher mixing rates for which greater homogenization of substrates is achieved.

09 BIOMASS FUELS↗

DOE OSTI2026

C–C Bond Formation during Electrochemical CO 2 Reduction on Pristine Cu(100) Unlikely to Involve Adsorbed CO at Any Potential

Formation of hydrocarbons containing two or more carbon atoms (C 2+ ) during heterogeneous electrochemical CO and CO 2 reduction (ECOR and ECO 2 R) only occurs, among pure metals, on Cu electrodes. Moreover, the activity and selectivity is facet dependent, with Cu(100) generally preferentially forming ethylene over methane. Previously, we found via quantum-mechanics-based modeling that, unlike standard density functional theory, more accurate correlated wavefunction methods predict that non-electroactive coupling pathways involving two adsorbed COs (*CO) or a *CO and a *COH to form C–C bonds on Cu(100) are kinetically inhibited, with the former also thermodynamically unfavorable. Here, we extend that embedded complete active space second order perturbation theory (ECASPT2) study, further showing that electrochemical coupling of two *COs to form an anionic dimer [OC*–*CO] (1+δ)– , followed by protonation to form [OC*–*COH] δ− , is not kinetically competitive with the reduction of *CO to *COH at relevant ECO/CO 2 R potentials. Our simulations therefore suggest that the ability of Cu(100) to electrochemically synthesize C 2+ molecules from CO and CO 2 is unlikely to be via *CO, at least on pristine Cu(100). Instead, hydrogenated CO species (*COH, *CH x OH, or *CH x ) are most likely to be the key intermediates in C–C bond formation.

Martirez, John Mark P. [Princeton Plasma Physics L↗

DOE OSTI2025

Impact of Pendant Amine Basicity on Electrochemically-Promoted Cobalt Hydride Formation: Kinetic and Mechanistic Analysis

Here, we report the role of pendant amine basicity on the proton-coupled electron transfer (PCET) reactivity for the conversion of [Co III Cp(P Ph 2 N R 2 )(CH 3 CN)] 2+ complexes to [HCo III Cp(P Ph 2 N R 2 )] + , which is a key transformation involved in catalytic CO 2 conversion to formate and in H 2 evolution. Three complexes were studied, where the amine substituent (R) varies from benzyl, methoxyphenyl, or phenyl. In previous work on the benzyl system, we showed that the amine on the P Ph 2 N Bn 2 ligand serves as a kinetically accessible protonation site and enables three participating hydride formation mechanisms. In this work, a combination of electrochemical measurements and theoretical calculations were used to show that the electronic donation at the pendant amine influences the accessible PCET mechanism and proton transfer kinetics related to cobalt hydride formation under analogous reaction conditions. Notably, the amine with the most electron-donating substituent correlates to the lowest barrier for amine protonation, and specific cobalt hydride formation mechanisms can be shut off for the amine with the least electron-donating substituent. The mechanistic and kinetic changes upon modulation of the amine substituent have great implications for overall catalytic efficiency and selectivity, especially to generate the cobalt hydride intermediate involved in selective CO 2 reduction to formate. This work shows how to exploit kinetic basicity using ligand-cooperative design to facilitate PCET reactions involved in energy related transformations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2022

A Unified Approach to Decarboxylative Halogenation of (Hetero)aryl Carboxylic Acids

Aryl halides are a fundamental motif in synthetic chemistry, playing a critical role in metal-mediated cross-coupling reactions and serving as important scaffolds in drug discovery. Although thermal decarboxylative functionalization of aryl carboxylic acids has been extensively explored, the scope of existing halodecarboxylation methods remains limited, and there currently exists no unified strategy that provides access to any type of aryl halide from an aryl carboxylic acid precursor. Herein, we report a general catalytic method for direct decarboxylative halogenation of (hetero)aryl carboxylic acids via ligand-to-metal charge transfer. This strategy accommodates an exceptionally broad scope of substrates. Here, we leverage an aryl radical intermediate toward divergent functionalization pathways: (1) atom transfer to access bromo- or iodo(hetero)arenes or (2) radical capture by copper and subsequent reductive elimination to generate chloro- or fluoro(hetero)arenes. The proposed ligand-to-metal charge transfer mechanism is supported through an array of spectroscopic studies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2019

Mechanistic studies of a “Declick” reaction

A kinetic analysis of a “declick” reaction is described. Compound 1, previously reported to couple an amine and a thiol (i.e. “click”) under mild aqueous conditions to create 2, undergoes release of the unaltered coupling partners upon triggering with dithiothreitol (DTT). In the study reported herein various aniline derivatives possessing para-electron donating and withdrawing groups were used as the amines. UV/vis spectroscopy of the declick reaction shows time-dependent spectra lacking isosbestic points, implying a multi-step mechanism. Global data fitting using numerical integration of rate equations and singular value decomposition afforded the spectra and time-dependence of each species, as well as rate constants for each step. The kinetic analysis reveals a multi-step process with an intermediate where both thiols of DTT have added prior to expulsion of the aniline leaving group, followed by rearrangement to the final product. Hammett plots show a negative rho value on two of the steps, indicating positive charge building (i.e. reduction of a negative charge) in the step leading to the intermediate and its ratedetermining breakdown. Overall, the kinetic study reported herein gives a complete mechanistic picture of the declick reaction.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2018

Properties of advanced coupled-cluster Green's function

We present an extension of the analysis previously applied to the retarded part of the coupled cluster (CC) Green's function to its advanced part. In analogy to our earlier studies for the retarded part, we demonstrate that the advanced CC Green's function is expressed in terms of connected diagrams only, which is a direct consequence of algebraic form of equations satisfied by CC amplitudes. We also demonstrate that omega-derivatives of the advanced CC Green's function can be calculated analytically and can be expressed in terms of connected diagrams only. We analyze the structure of connected diagrams and the role of intermediate operators which satisfy electron affinity equation-of-motion CC type conditions.

electronic structure theory↗

DOE OSTI2017

Dynamics of the Bingham Canyon rock avalanches (Utah, USA) resolved from topographic, seismic, and infrasound data: Bingham Canyon Rock Avalanches

The 2013 Bingham Canyon Mine rock avalanches represent one of the largest cumulative landslide events in recorded U.S. history and provide a unique opportunity to test remote analysis techniques for landslide characterization. We combine aerial photogrammetry surveying, topographic reconstruction, numerical runout modeling, and analysis of broadband seismic and infrasound data to extract salient details of the dynamics and evolution of the multiphase landslide event. Our results reveal a cumulative intact rock source volume of 52 Mm 3 , which mobilized in two main rock avalanche phases separated by 1.5 h. We estimate that the first rock avalanche had 1.5–2 times greater volume than the second. Each failure initiated by sliding along a gently dipping (21°), highly persistent basal fault before transitioning to a rock avalanche and spilling into the inner pit. The trajectory and duration of the two rock avalanches were reconstructed using runout modeling and independent force history inversion of intermediate-period (10–50 s) seismic data. Intermediate- and shorter-period (1–50 s) seismic data were sensitive to intervals of mass redirection and constrained finer details of the individual slide dynamics. Back projecting short-period (0.2–1 s) seismic energy, we located the two rock avalanches within 2 and 4 km of the mine. Further analysis of infrasound and seismic data revealed that the cumulative event included an additional 11 smaller landslides (volumes ~10 4 –10 5 m 3 ) and that a trailing signal following the second rock avalanche may result from an air-coupled Rayleigh wave. These results demonstrate new and refined techniques for detailed remote characterization of the dynamics and evolution of large landslides.

58 GEOSCIENCES↗

DOE OSTI2023

Temporally Stable Supramolecular Polymeric Salts Enabling High-Performance 3D All-Aromatic Polyimide Lattices

Vat photopolymerization (VP) Additive Manufacturing (AM), in which UV light is selectively applied to cure photo-active polymers into complex geometries with micron-scale resolution, has a limited selection of aliphatic thermoset materials that exhibit relatively poor thermal performance. Ring-opening dianhydrides with acrylate-containing nucleophiles yielded diacrylate ester-dicarboxylic acids that enabled photo-active polyimide (PI) precursors, termed polysalts, upon neutralization with an aromatic diamine in solution. In situ FTIR spectroscopy coupled with a solution and photo-rheological measurements revealed a previously unknown time-dependent instability of 4,4'-oxydianiline (ODA) polysalts due to an aza-Michael addition. Replacement of the electron-donating ether-containing diamine with an electron withdrawing sulfone-containing monomer, e.g., 4,4'-diaminodiphenyl sulfone (DDS), prohibited the aza-Michael addition of the aromatic amine to the activated acrylate double bond. Novel DDS polysalt photocurable solutions are similarly analyzed and validated long-term stability, which enabled reproducible printing of polyimide organogel intermediates. Subsequent VP AM afforded 3-dimensional (3D) structures of intricate complexity and excellent surface finish, as demonstrated with scanning electron microscopy. In addition, the novel PMDA-HEA/DDS solution enabled the production of the first beam latticed architecture comprised of all-aromatic polyimide. Finally, the versatility of a polysalt platform for multi-material printing is further demonstrated by printing parts with alternating polysalt compositions.

36 MATERIALS SCIENCE↗