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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 1,441 records · Page 80
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Ultrafast Formation of Charge Transfer Trions at Molecular‐Functionalized 2D MoS 2 Interfaces

Abstract In this work, we investigate trion dynamics occurring at the heterojunction between organometallic molecules and a monolayer transition metal dichalcogenide (TMD) with transient electronic sum frequency generation (tr‐ESFG) spectroscopy. By pumping at 2.4 eV with laser pulses, we have observed an ultrafast hole transfer, succeeded by the emergence of charge‐transfer trions. This observation is facilitated by the cancellation of ground state bleach and stimulated emission signals due to their opposite phases, making tr‐ESFG especially sensitive to the trion formation dynamics. The presence of charge‐transfer trion at molecular functionalized TMD monolayers suggests the potential for engineering the local electronic structures and dynamics of specific locations on TMDs and offers a potential for transferring unique electronic attributes of TMD to the molecular layers.

Jing, Yuancheng↗
DOE OSTI2022

Growth Optimization and Device Integration of Narrow‐Bandgap Graphene Nanoribbons

Abstract The electronic, optical, and magnetic properties of graphene nanoribbons (GNRs) can be engineered by controlling their edge structure and width with atomic precision through bottom‐up fabrication based on molecular precursors. This approach offers a unique platform for all‐carbon electronic devices but requires careful optimization of the growth conditions to match structural requirements for successful device integration, with GNR length being the most critical parameter. In this work, the growth, characterization, and device integration of 5‐atom wide armchair GNRs (5‐AGNRs) are studied, which are expected to have an optimal bandgap as active material in switching devices. 5‐AGNRs are obtained via on‐surface synthesis under ultrahigh vacuum conditions from Br‐ and I‐substituted precursors. It is shown that the use of I‐substituted precursors and the optimization of the initial precursor coverage quintupled the average 5‐AGNR length. This significant length increase allowed the integration of 5‐AGNRs into devices and the realization of the first field‐effect transistor based on narrow bandgap AGNRs that shows switching behavior at room temperature. The study highlights that the optimized growth protocols can successfully bridge between the sub‐nanometer scale, where atomic precision is needed to control the electronic properties, and the scale of tens of nanometers relevant for successful device integration of GNRs.

36 MATERIALS SCIENCE↗
NASA NTRS1986

Adhesion and wear resistance of materials

Recent studies into the nature of bonding at the interface between two solids in contact or a solid and deposited film have provided a better understanding of those properties important to the adhesive wear resistance of materials. Analytical and experimental progress are reviewed. For simple metal systems the adhesive bond forces are related to electronic wave function overlap. With metals in contact with nonmetals, molecular-orbital energy, and density of states, respectively can provide insight into adhesion and wear. Experimental results are presented which correlate adhesive forces measured between solids and the electronic surface structures. Orientation, surface reconstruction, surface segregation, adsorption are all shown to influence adhesive interfacial strength. The interrelationship between adhesion and the wear of the various materials as well as the life of coatings applied to substrates are discussed. Metallic systems addressed include simple metals and alloys and these materials in contact with themselves, both oxide and nonoxide ceramics, diamond, polymers, and inorganic coating compounds, h as diamondlike carbon.

Buckley, D. H.↗
NASA NTRS2022

Vibrational and Rovibrational Spectroscopy Applied to Astrochemistry

The detection of molecules in astrophysical environments almost always requires remote sensing. While radioastronomical observation and associated rotational spectroscopy are powerful astronomical tools, infrared spectral analysis provides a unique means of examining the observable universe, especially for molecules where permanent dipole moments are small or even non-existent. The molecular vibrations of small molecules are now able to be modeled via quantum chemistry and electronic structure theory conjoined to vibrational analysis to within spectroscopic accuracy in many cases. This chapter will showcase this success and build upon it to show how such advances are now being leveraged to describe molecular vibrations for molecules containing dozens of atoms, electronically excited states, "hot bands," exoplanetary atmospheric opacity data, and even emission of polycyclic aromatic hydrocarbons. All of these are required to prune the interstellar spectral garden of its "weeds" in search of "flowers" that will provide the necessary fingerprints for astronomers to be able to probe the heavens for its past, present, and future secrets.

Ryan C. Fortenberry↗
DOE OSTI2023

Identification of novel organic polar materials: A machine learning study with importance sampling

Recent advances in the synthesis of polar molecular materials have produced practical alternatives to ferroelectric ceramics, opening up exciting new avenues for their incorporation into modern electronic devices. However, in order to realize the full potential of polar polymer and molecular crystals for modern technological applications, it is paramount to assemble and evaluate all the available data for such compounds, identifying descriptors that could be associated with an emergence of ferroelectricity. In this paper, we utilized data-driven approaches to judiciously shortlist candidate materials from a wide chemical space that could possess ferroelectric functionalities. A machine learning study with importance sampling was employed to address the challenge of having a limited amount of available data on already-known organic ferroelectrics. Sets of molecular- and crystal-level descriptors were combined with a Random Forest Regression algorithm in order to predict the spontaneous polarization of the shortlisted compounds. First-principles simulations were performed to further validate the predictions obtained from the machine learning model.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Quantum Embedding Theory for Strongly Correlated States in Materials

Quantum embedding theories are promising approaches to investigate strongly correlated electronic states of active regions of large-scale molecular or condensed systems. Notable examples are spin defects in semiconductors and insulators. We present a detailed derivation of a quantum embedding theory recently introduced, which is based on the definition of effective Hamiltonians. The effect of the environment on a chosen active space is accounted for through screened Coulomb interactions evaluated using density functional theory. Importantly, the random phase approximation is not required, and the evaluation of virtual electronic orbitals is circumvented with algorithms previously developed in the context of calculations based on many-body perturbation theory. In addition, we generalize the quantum embedding theory to active spaces composed of orbitals that are not eigenstates of Kohn–Sham Hamiltonians. Finally, we report results for spin defects in semiconductors.

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

rlmolecule: A library for general-purpose material and molecular optimization using AlphaZero-style reinforcement learning

This library includes in-progress code for the optimization of materials and molecules using reinforcement learning. This project seeks to develop a generalized machine learning approach for optimizing targeted, and often complex, functional properties over the space of possible material structures, allowing faster identification of promising candidates. Electronic and transport properties of materials are determined by their molecular structure (for molecules) or their crystal structure (for in-organic crystalline materials). The atomic composition, bonding, and 3-D-spatial arrangement in these systems therefore represent a vast, discontinuous search space for optimal candidates. This library implements AlphaZero style reinforcement learning applied to two worked examples: the optimization of stable organic radicals for redox flow batteries, and the determination of stable electrolyte species for solid state batteries. The current code contains proof-of-concept results run on the Eagle HPC system, while the completed package will be a flexible tool for material optimization across of number of energy-relevant fields, which leverages cloud compute resources for the majority of the computational heavy lifting.

Biagioni, David↗
NASA NTRS1994

Collisional-Radiative Nonequilibrium and Precursor Effects in a Nitrogen Shock Wave

Improvements to a plasma code with a Collisional-Radiative (CR) non-equilibrium model are made, allowing for a more accurate description of the physical processes. The code allows for non-Boltzmann distributions of the electronic excited states by convecting separately each excited state, as a pseudo-specie. Each molecular state has also its own vibrational temperature, while a global rotational temperature is assumed. The free electron temperature is different from those of the excited states, and the electron heat conduction is also included. The CR model also uses a unique coupling between chemistry and vibrational energy (C-V coupling), which is fully coherent, and has the property of establishing thermal equilibrium as well as chemical equilibrium, on its own. We have also included a coupling between electronic excitations and vibrational energy (X-V coupling), which can have a strong influence on the vibrational temperature of some states. The recent improvements include the multi- temperature dependence of the chemical rates for associative ionization, as well as the estimation of the internal energies transferred during this process. Additionally, the distribution of energy into different translational modes (electron and heavy particles) is now correctly modeled. This provides a very rapid heating mechanism for the free electrons, since it is found that the electrons are generated with an average thermal energy of the same order as the heavy particle translational energy. This effect was observed by Gorelov et al in a recent paper, and lead to pronounced peaks in electron temperature immediately behind the shock. We will attempt ro reproduce this phenomenon. The last modification concerns the inclusion of the radiative terms into the calculations, thus enabling us to observe the effect of radiative losses and radiation transport. Preliminary tests have shown that the radiative losses are not negligible, i.e. the shock velocity drops when the radiative emission is included. In addition, we have observed some precursor excitation and ionization phenomena. These may be important at high shock velocities, and this will be investigated in detail. Precursor phenomena were also observed (in air) by Gorelov et al, and our results (for pure nitrogen) will be qualitatively compared with theirs.

Cambier, Jean-Luc↗
NASA NTRS1974

Vibrationally excited nitrogen in stable auroral red arcs and its effect on ionospheric recombination

The time-dependent continuity equations, including diffusion, were solved for the first six energy levels of molecular nitrogen for conditions in the thermosphere corresponding to stable auroral red (SAR) arcs. The results show that molecular nitrogen is excited vibrationally to the degree that the rate constant for the ionospheric loss process, O(+) + N2 yields NO(+) + N, is increased by as much as a factor of 7.6 at F2 region altitudes. It was found that deviations from the energetically equivalent Boltzmann distribution were large, causing the rate constant to be as much as 1.6 times the rate constant calculated for the Boltzmann distribution. These results indicate that SAR arc intensities as small as 58 R can produce noticeable increases in the ionosphere ion-atom interchange reaction rate and hence in the rate of loss of ionospheric electrons. It is suggested that the observed decrease of electron density in the F2 region in SAR arcs can probably be explained by enhanced reaction rates for ion-atom interchange between O(+) and N2 caused by vibrational excitation of molecular nitrogen by electron impact.

Newton, G. P.↗
DOE OSTI2025

Orbital Engineering Band Degeneracy in a Dual-Square Carbon-Oxide Framework

Electron band degeneracies in momentum space give rise to exotic quantum phenomena that have sparked intense interest in condensed matter physics and materials science. Nodal-lines─isolines in k-space formed by the incidental touching of two bands that share the same energy but belong to discrete eigenstates─arise in the presence of symmetries that preclude effective hybridization. Despite recent advances in the design, bottom-up assembly, and engineering of exotic electronic states in graphene nanomaterials, the extension of this approach to access synthetic two-dimensional (2D) quantum materials derived from metal- or covalent-organic frameworks (COFs) has lagged behind. Here we present a molecular orbital engineering approach for designing and fabricating an edge-centered dual square lattice within a π-conjugated 2D-tetraoxa[8]circulene (2D-TOC) COF. First-principles calculations and scanning tunnelling spectroscopy reveal the emergence of Frontier states at the center of a 3 × 3 lattice that give rise to Dirac nodal-lines in 2D-TOC. Our findings not only provide a general guide for the design of conjugated COFs with custom tailored electronic properties from molecular fragments but enable the exploration of emergent topological phenomena in synthetic 2D materials with potential application for high-speed, low-power data processing, transmission, and storage.

Dirac nodal line semimetal↗
DOE OSTI2024

Electric dipole moments in 5+3 flavor weak effective theory

A fully generic treatment of electric dipole moments (EDMs) is presented in the CP-violating and flavor-conserving weak effective field theory (WET) with five flavors of quarks and three flavors of leptons. We systematically analyze leading contributions to EDMs originating from QCD and QED renormalization group running between the electroweak scale and low energy scales of about 2 GeV. We include the full one-loop anomalous dimension and a subset of two-loop corrections, as well as threshold corrections at the bottom, charm and τ masses. This allows us to derive master formulae in the space of generic WET for the neutron and proton EDMs, for EDMs of diamagnetic atoms, and for the precession frequencies constrained in molecular EDM experiments, from which bounds on the electron EDM are extracted. In particular, our master formulae capture the contributions of WET CP-violating operators with heavy quark and lepton flavors. As an application, we study EDM constraints on the Yukawa couplings of the Higgs boson, in both the linear and non-linear realizations of electroweak symmetry breaking.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2025

Spectral emission characteristics near 646 nm and plasma properties of laser-induced plasma of gaseous uranium hexafluoride

We present a detailed investigation of the temporal evolution of line and continuum emissions in laser-induced breakdown spectroscopy (LIBS) of gaseous uranium hexafluoride (UF 6 ), focusing on the spectral region near 646 nm. Spectral emission features, signal-to-background ratios (SBRs) of selected uranium lines, and spectral linewidths were examined under varying UF 6 pressures (15–60 Torr) and laser pulse energies (10–60 mJ). Higher pressures and pulse energies enhanced continuum emission and reduced SBRs but did not cause significant spectral congestion. Additional studies with the use of different laser systems, including nanosecond-pulsed Nd:YAG lasers (at fundamental and various harmonics) and a femtosecond-pulsed Ti:sapphire laser, revealed long-lived plasma continua in all cases. This persistent continuum is attributed to a pseudo-continuum from overlapping molecular emissions, as its intensity scales linearly with electron number density, deviating from the expected quadratic dependence of classical ion–electron interactions for free-free and free-bound continuum emission. Based on plasma persistence time, SBR, U II/U I intensity ratios, and electronic excitation temperature, no fundamental advantage was found for femtosecond-pulsed lasers over conventional nanosecond-pulsed ones for UF 6 enrichment assay with direct LIBS measurement.

Laser-induced breakdown spectroscopy↗
DOE OSTI2025

Growth and Characterization of Epitaxial FeWO 4 Thin Films with Controlled Oxygen Stoichiometry

Here, we report the growth of single-phase epitaxial FeWO 4 thin films, using plasma-assisted molecular beam epitaxy, and investigate structural, optical, and electronic properties. The FeWO 4 films grow in (100) orientation on c-plane sapphire (0001) substrates and exhibit 3 rotational twin variants where FeWO 4 [001] is aligned to sapphire [100] equivalent in-plane directions. X-ray diffraction measurements indicate that the epitaxial FeWO 4 (100) structure is optimized when 80-100 W of rf power is applied to an atomic oxygen source during growth, yielding films with minimal strain and impurity phases or other orientations. In films grown with 120 W of rf power, FeWO 4 crystallites develop inhomogeneous and homogeneous strains and are potentially contaminated with Fe 3+ oxide phase impurities. In films grown with 60 W of rf power, FeWO 4 crystallites do not form fully epitaxial layers. X-ray photoelectron spectroscopy indicates that the structural changes are correlated with the Fe 3+ /Fe 2+ oxidation state ratio increasing from 0.6-1.4 with rf power from 60-120 W. X-ray fluorescence spectroscopy indicates that the Fe/W composition ratio is also increasing from 1.1-1.8 with rf power from 60-120 W. Ultraviolet and visible optical absorption spectra indicate a 1.8 ± 0.1 eV band gap with an additional interband absorption feature at 3.1 ± 0.1 eV in the 80-100 W films, with similar onsets observed in the 60 W films. In the 120 W films, the higher lying transition is shifted to 2.7 ± 0.1 eV due to the Fe 3+ enrichment. Electrical resistivity decreases over 2 orders of magnitude with oxidation from 10 4 -10 5 Ω cm in 60 W films to 120 ± 10 Ω cm in 120 W films. Thermopower measurements show p-type to n-type conductivity conversion when oxidation states shift from Fe 2+ majority in the 100 W films to Fe 3+ majority in the 120 W films. We conclude that electron polaron hopping driven by Fe 3+ is a dominant transport mechanism and a source of n-type conductivity in overoxidized FeWO 4 films.

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

Zero-Field NMR and Millitesla-SLIC Spectra for >200 Molecules from Density Functional Theory and Spin Dynamics

NMR is usually performed at magnetic fields of 1 T and above to obtain sufficient sensitivity and spectral dispersion to identify chemicals based on chemical shifts and J couplings. At lower fields, the advent of hyperpolarization technologies and sensitive detectors can address sensitivity concerns. However, it remains disputed whether spectral signatures at zero and ultra-low fields are sufficient for chemical identification. Here, we report an all–electron DFT-based batch calculation of J-coupling constants, which are used to generate J coupling NMR spectra at zero field and 6.5 mT for over 200 small molecules. In the developed computational tool chain, we first used the all-electron FHI-aims code to calculate the molecular J couplings and chemical shifts. We then fed the calculated NMR parameters into the NMR simulation package SPINACH to simulate both heteronuclear J coupling spectra at zero-field, and homonuclear J coupling spectra as spin-lock induced crossing (SLIC) spectra at ultra-low field (6.5 mT). The resulting spectra demonstrate that zero and ultra-low field NMR spectra can represent unique identifiers of chemical structure for small molecules.

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

Quadratic Unitary Coupled-Cluster Singles and Doubles Scheme: Efficient Implementation, Benchmark Study, and Formulation of an Extended Version

An efficient implementation of the quadratic unitary coupled-cluster singles and doubles (qUCCSD) scheme for calculations of electronic ground and excited states using an unrestricted molecular spin–orbital formulation and an efficient tensor contraction library is reported. The accuracy of the qUCCSD scheme and the efficiency of the present implementation are demonstrated using extensive benchmark calculations of excitation energies and an application to S o → S 1 vertical excitation energies for cis- and trans-4a,4b-dihydrotriphenylene. The qUCCSD scheme has been shown to provide improved excitation energies compared with the UCC3 scheme formulated based on perturbation theory. Here, a UCC truncation scheme that can provide excitation energies correct through the fourth order is also presented to further improve the accuracy of the qUCCSD scheme.

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

Gas-Phase Study of the Elementary Reaction of the D1-Ethynyl Radical (C 2 D; X 2 Σ + ) with Propylene (C 3 H 6 ; X 1 A') under Single-Collision Conditions

The bimolecular gas-phase reactions of the D1-ethynyl radical (C 2 D; X 2 Σ + ) with propylene (C 3 H 6 ; X 1 A’) and partially substituted D3-3,3,3-propylene (C 2 H 3 CD 3 ; X 1 A’) were studied under single collision conditions utilizing the crossed molecular beams technique. Combining our laboratory data with electronic structure and statistical calculations, the D1-ethynyl radical is found to add without barrier to the C1 and C2 carbons of the propylene reactant, resulting in doublet C 5 H 6 D intermediate(s) with lifetime(s) longer than their rotational period(s). These intermediates undergo isomerization and unimolecular decomposition via atomic hydrogen loss through tight exit transition states forming predominantly cis/trans-3-penten-1-yne ((HCC)CH=CH(CH 3 )) and to a minor amount 3-methyl-3-buten-1-yne ((HCC)C(CH 3 )=CH 2 ) via overall exoergic reactions. Although the title reaction does not lead to the cyclopentadiene molecule (c-C 5 H 6 , X 1 A 1 ), high temperature environments can convert the identified acyclic C 5 H 6 isomers through hydrogen atom assisted isomerization to cyclopentadiene (c-C 5 H 6 , X 1 A 1 ). Since both the ethynyl radical and propylene reactants have been observed in cold interstellar environments such as TMC-1 and the reaction is exoergic and all barriers lie below the energy of the separated reactants, the these C 5 H 6 product isomers are predicted to form in those low temperature regions.

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

Water-Soluble Copper(I) Hydroxide Catalyst and Its Formation in Ligand-Free Suzuki–Miyaura Cross-Coupling Reactions

Copper has emerged as an alternative metal for metal-catalyzed cross-coupling reactions due to its low cost, readily availability, and low toxicity. Here this article reports a water-soluble active molecular catalyst and its formation in the ligand-free Suzuki–Miyaura (SM) cross-coupling reactions with copper iodide as the precatalyst in aqueous solutions. The SM coupling is homogeneous in nature, and the molecular catalyst is Cu(OH) in its singlet electronic state as identified by experimental and computational UV–vis absorption spectroscopy. The Cu(OH) catalyst is generated through the leaching of oval-shaped Cu 2 O nanoparticles, which are characterized with X-ray Auger electron spectroscopy, X-ray absorption spectroscopy, and transmission electron microscopy. The soluble Cu(OH) species is stable for at least 4 weeks under ambient conditions.

cross-coupling↗
DOE OSTI2024

A dual-species Rydberg array

Large-scale Rydberg atom arrays are used for highly coherent analogue quantum simulations and for digital quantum computations. However, advanced quantum protocols, such as quantum error correction, require midcircuit qubit operations, including the replenishment, reset and read-out of a subset of qubits. A compelling strategy for unlocking these capabilities is a dual-species architecture in which a second atomic species is controlled independently and entangled with the first through Rydberg interactions. Here, we realize a dual-species Rydberg array consisting of rubidium and caesium atoms and explore regimes of interactions and dynamics not accessible in single-species architectures. We achieve enhanced interspecies interactions by electrically tuning the Rydberg states close to a Förster resonance. In this regime, we demonstrate an interspecies Rydberg blockade and implement a quantum state transfer from one species to another. We then generate a Bell state between Rb and Cs hyperfine qubits through an interspecies controlled-phase gate. Finally, we combine interspecies entanglement with a native midcircuit read-out to achieve quantum non-demolition measurements.

atomic and molecular interactions with photons↗