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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 289 records · Page 16
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Investigation of pyruvic acid photolysis at the air-liquid interface as a source of aqueous secondary organic aerosols

Pyruvic acid (PA) is a ubiquitous 2-oxocarboxylic acid in the atmosphere. Its photochemical process at the air-liquid (a-l) interface has been suggested as an important source of aqueous secondary organic aerosols. Here, we investigated the photochemical reaction pathways of PA at the a-l interface using synchrotron-based vacuum ultraviolet single-photon ionization mass spectrometry (VUV SPI-MS) coupled with the System for Analysis at the Liquid Vacuum Interface (SALVI) microreactor. Results from mass spectral analysis and the determination of appearance energies (AEs) indicate that photolysis of PA can generate radicals, then they recombine with carboxylic acids and simple molecular oligomers. Furthermore, the preliminary products could form larger oligomers via radical reaction or esterification in the presence of hydroxyl and carboxyl functional groups. Mass spectral comparison shows that most photochemical reactions would complete within 4 h. The expanded photochemistry-driven reaction flowchart of PA is proposed based on the newly discovered products. Our results reveal that the interfacial PA photochemical reactions have different mechanisms from the bulk liquid due to the interfacial properties, such as molecular density, composition, and ion concentration. Our findings show that in situ mass spectral analysis with bright photon ionization is useful to elucidate the contribution of a-l interfacial reactions leading to aqSOA formation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

A Bis(arenesulfonyl) Peroxide, an Ambient-Stable Oxidant, Is a Strong p-Dopant for Organic Semiconductors

Strong p-dopants are required to dope high-ionization energy organic semiconductors for a variety of potential applications, but strong, simple one-electron oxidants are typically sensitive to reduction by atmospheric moisture and thus challenging to store or handle. Here we show that bis(3,5-bis(trifluoromethyl)benzenesulfonyl) peroxide─a dimer formed by two highly oxidizing radicals─can function as a water-stable yet powerful oxidant, cleanly reacting with some organic semiconductors to form two radical cations and two 3,5-bis-(trifluoromethyl)benzenesulfonate anions, although in other cases sulfonylation reactions can also occur. Notably, this peroxide is capable of p-doping the high-ionization energy polymer poly[(9,9-dioctylfluorene-2,7-diyl)- alt -(benzo[2,1,3]thiadiazol-4,7-diyl)] (F8BT) to afford electrical conductivities of up to 0.03 S cm –1 , while its use with electron-rich poly(3,4-dialkoxythiophene-2,5-diyl) derivatives can afford values up to 100 S cm –1 . Quantum-chemical calculations reveal the peroxide oxidant behaves in a fashion mirroring that of relatively oxygen-stable, but highly reducing, n-dopants that have been developed based on dimers of organic radicals or organometallic sandwich compounds.

doping↗
DOE OSTI2026

Revealing Hidden Quinones Through Diagnostic MS² Fragmentation of Peptide–Quinone Adducts

Quinones are redox-active components of natural organic matter that mediate electron transfer and influence biogeochemical processes, but many quinones in pyrogenic organic matter (PyOM) remain unresolved because they ionize poorly by mass spectrometry. Here, we present a peptide-tagging approach to improve detection of cysteine-reactive electrophiles in PyOM, with quinones expected to be a dominant subset based on reaction chemistry and selectivity experiments. A cysteine-containing peptide was used to form Michael-addition adducts, enhancing electrospray ionization and enabling untargeted screening by high-performance liquid chromatography-high-resolution tandem mass spectrometry. The method was benchmarked with five quinone standards and applied to extracts from charred plant material as a discovery-level screen for cysteine-reactive targets. We identified 98 quinone-candidate adducts (mean neutral mass ~603 Da), of which more than 70% were not detectable in native MS1 data. Among formula-assigned features, hidden quinone candidates had median (O+N)/C of 0.391 and normalized oxidation state of carbon of -0.281, consistent with relatively low polarity and low oxidation state. These results reveal a previously inaccessible pool of hidden redox-active compounds in PyOM and provide a framework for prioritizing quinone-like electrophiles for confirmation and incorporation into models of fire-driven biogeochemical cycling.

LC-MS/MS↗
DOE OSTI2024

An Orbital Basis Set for Double Photoionization of Atoms and Molecules

The ab initio theoretical treatment of one-photon double photoionization processes has been limited to atoms and diatomic molecules by the challenges posed by large grid-based representations of the double ionized continuum wave function. To provide a path for extensions to polyatomics, an energy-adapted orbital basis approach is demonstrated that reduces the dimensions of such representations and simultaneously allows larger time steps in time-dependent computational descriptions of double ionization. Additionally, an algorithm that exploits the diagonal nature of the two-electron integrals in the grid basis and dramatically accelerates the transformation between grid and orbital representations is presented. Excellent agreement between the present results and benchmark theoretical calculations is found for H – and Be atoms, as well as the hydrogen molecule, including for the triply differential cross sections that relate the angular distribution and energy sharing of all of the particles in the molecular frame.

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

An Experimental and Theoretical Study of the Valence Shell Electronic Structure of Nitromethane

Vibrationally resolved CH 3 NO 2 and CD 3 NO 2 photoelectron spectra and angular distribution parameters, β, have been measured in the photon energy range 20–80 eV. This allows a comprehensive investigation of conflicting literature interpretations of the two outermost photoelectron bands, complemented by high-level calculations characterizing the three O lone-pair-based orbital ionizations expected in this region. Franck–Condon simulations allow the regular vibrational progressions observed at the beginning of the first and second bands to be assigned as predominantly modes v 5 and v 6 of the D 0 and D 2 cation states, respectively. Irregular structuring observed midband in both bands is attributed to avoided crossings between the adiabatic D 0 /D 1 and D 1 /D 2 states as identified in potential surface cuts taken along the v 5 and v 6 normal mode coordinates. The associated D 0 /D 1 and D 1 /D 2 conical intersections were located and characterized, allowing possible vibronic coupling and its impact on the photoelectron spectra of the D 0 , D 1 , and D 2 states to be discussed. This helps rationalize the apparently missing D 1 ionization in this region, although some contribution by this state may be identifiable in the β-parameter spectra. Theoretical analysis of the complete valence region spectrum identifies the early breakdown of the independent electron model beyond these first two bands.

Powis, Ivan [University of Nottingham (United King↗
DOE OSTI2026

Transient Pulse-Response Time-of-Flight Mass Spectrometry for Complex, Deactivating Heterogeneous Catalytic Systems: Application to Ethane Dehydroaromatization

The study of complex, multistep bond-forming and -breaking reactions in heterogeneous catalytic systems often encounters challenges associated with the involvement of large numbers of intermediates among branching pathways. Kinetic information obtained from traditional steady-state measurements can be complemented with that from time-resolved methods to uncover details of the underlying chemistry. Herein, we describe an approach for tracking the complete time-resolved chemical composition (ca. 4–200 u) of a reactor effluent in response to a reactant pulse. We use a six-port rotary valve with a metered sampling loop to pulse reactants at ambient pressure into a flow reactor packed with a catalyst bed within the isothermal region of a heated furnace. The temporal evolution of effluent species is tracked using time-resolved molecular-beam time-of-flight mass spectrometry. We highlight the possibilities that this method has to offer by studying the complex bifunctional mechanism of ethane dehydroaromatization over an HZSM-5-supported platinum catalyst. We demonstrate that energy-tunable ionization sources, which facilitate isomer resolution, enable the measurement of the full mass spectral time-dependent system response. This includes the evolution of major products and mechanistically relevant reactive intermediates such as 1,3-butadiene and cyclopentadiene; these species have not previously been observed from this reaction. In additional studies, we also assess the role of platinum in the catalyst by examining temporal responses to ethane and ethylene feeds. Results show that two temporally distinct formation pathways exist for methane and benzene, and that their importance depends on both catalyst composition and reactant identity. Additionally, characteristics of catalyst deactivation are uniquely observable in the time-resolved mass spectral response, including the selective deactivation of a benzene formation pathway. The combination of time-of-flight mass spectrometry with tunable ionization enables the simultaneous observation of all effluents in a complex mixture of intermediates with isomer/isobar differentiation capabilities that can be applied to any complex reaction system.

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

Crystalline Peptoid Nanofibers with a Single-Unit Cell Cross Section

Ultranarrow crystalline one-dimensional nanostructures formed from soft materials facilitate precise structural control in nanomaterial design, which is essential for biomedicine and nanotechnology applications. Systematic control of their hierarchical structure is challenging due to the complexities of simultaneously manipulating multiple noncovalent interactions at such small scales. We employed a polypeptoid crystal motif as a supramolecular synthon to engineer ultranarrow crystalline nanofibers constrained to a single lattice axis by incorporating a single ionizable side chain into the hydrophobic core of a nanosheet-forming peptoid. Cryogenic transmission electron microscopy of the nanofibers revealed detailed molecular arrangements of a unit-cell cross-section and the presence of distinct pH-dependent lattice isoforms that resulted in morphological transformations. Molecular dynamics simulations demonstrated that the ionizable side chain plays a critical role in changing the local conformation of the unit cell, which further impacts the dimensionality of hierarchical structures. Moreover, these fibers were readily functionalized with biological ligands to afford one-dimensional (1D) protein arrays. This approach for the high-precision bottom-up assembly of ultranarrow 1D nanostructures offers significant potential for developing novel biomimetic nanostructures.

Lee, Yen Jea↗
DOE OSTI2026

Comparing Liquid Vortex Capture & the Rapid Droplet Sampling Interface for Single Cell Mass Spectrometry

High-throughput single-cell mass spectrometry is a rapidly evolving field that requires innovative sampling and ionization techniques to balance speed, sensitivity, and reliability for metabolomic and lipidomic analyses. This study provides a comparative analysis of two cutting-edge ionization platforms for single-cell analysis: Liquid Vortex Capture (LVC) and Rapid Droplet Sampling Interface (RDSI). The performance was benchmarked by testing pharmaceuticals, EquiSPLASH, and single-cell experiments. RDSI demonstrated up to 100-fold improvements in sensitivity for drugs and lipids such as propranolol, amiodarone, atorvastatin, and phosphocholines in water and phosphate-buffered solutions. This was attributed to its low-flow rate operation (3 μL/min) and reduced dilution. Conversely, LVC excelled in handling higher liquid volumes with greater reproducibility due to its higher solvent flow rate (200 μL/min), enabling increased dilution, solubility, and cleaning. Single-cell uptake of atorvastatin incubated for 10 min, or amiodarone incubated for 24 h in HepG2 cells, similarly revealed up to 85-fold enhancement in sensitivity by RDSI for drugs and lipids. These findings highlight the potential of RDSI for enhancing sensitivity in single-cell drug monitoring and lipidomics.

Cahill, John [ORNL] (ORCID:0000000298664010)↗
DOE OSTI2024

The role of charge in microdroplet redox chemistry

In charged water microdroplets, which occur in nature or in the lab upon ultrasonication or in electrospray processes, the thermodynamics for reactive chemistry can be dramatically altered relative to the bulk phase. Here, we provide a theoretical basis for the observation of accelerated chemistry by simulating water droplets of increasing charge imbalance to create redox agents such as hydroxyl and hydrogen radicals and solvated electrons. We compute the hydration enthalpy of OH - and H + that controls the electron transfer process, and the corresponding changes in vertical ionization energy and vertical electron affinity of the ions, to create OH • and H • reactive species. We find that at ~ 20 - 50% of the Rayleigh limit of droplet charge the hydration enthalpy of both OH - and H + have decreased by >50 kcal/mol such that electron transfer becomes thermodynamically favorable, in correspondence with the more favorable vertical electron affinity of H + and the lowered vertical ionization energy of OH - . We provide scaling arguments that show that the nanoscale calculations and conclusions extend to the experimental microdroplet length scale. The relevance of the droplet charge for chemical reactivity is illustrated for the formation of H 2 O 2 , and has clear implications for other redox reactions observed to occur with enhanced rates in microdroplets.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Revealing ultrafast proton-transfer-mediated autoionization as a source of low-energy electrons in hydrogen-bonded systems

Ionizing radiation can trigger ultrafast proton transfer, a central mechanism in many chemical and biological functions, that in turn can enable or suppress electron relaxation processes and consequently cause abrupt changes in the reaction pathway. This study combines theory and experiment to probe ultrafast relaxation and dissociation in water dimers following inner- and outer-valence photoionization. By tracking electron and nuclear motion simultaneously, we reveal competing fragmentation pathways that produce low-energy electrons, which are key agents in radiation-induced chemistry, including DNA damage. While low-energy electrons are known to arise via intermolecular Coulombic decay, here we identify a faster relaxation mechanism gated by proton transfer following inner-valence ionization, which we call proton-transfer-mediated autoionization. Occurring within 10 femtoseconds, this process alters fragmentation outcomes, yielding either D 3 O + + OD + or D 2 O + + D 2 O + , depending on the interplay of proton migration and hydrogen back-transfer. Our findings underscore the intricate coupling between electronic and nuclear dynamics in hydrogen-bonded systems and establish proton-transfer-mediated autoionization as a significant pathway for low-energy electron generation.

Atomic and molecular interactions with photons↗
DOE OSTI2024

N-type molecular doping of a semicrystalline conjugated polymer through cation exchange

Control of electrical doping is indispensable in any semiconductor device, and both efficient hole and electron doping are required for many devices. In organic semiconductors, however, electron doping has been essentially more problematic compared to hole doping because in general organic semiconductors have low electron affinities and require dopants with low ionization potentials that are often air-sensitive. Here, we adapt an efficient molecular doping method, so-called ion-exchange doping, to dope electrons in a polymeric semiconductor. We initially reduce the polymeric semiconductor using one electron transfer from molecular dopants, and then the ionized dopants in the resulting air-unstable films are replaced with secondary ions via cation exchange. Improved ambient stability and crystallinity of the doped polymeric semiconductors are achieved when a specific bulky molecular cation was chosen as the secondary ion, compared to conventional methods. The presented strategy can overcome the trade-off relationship between reducing capability and ambient stability in molecular dopants, and a wider selection of dopant ions will help to realize ambient-stable electron conductors.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Ultrafast dynamics of fluorene initiated by highly intense laser fields

Here, we present an investigation of the ultrafast dynamics of the polycyclic aromatic hydrocarbon fluorene initiated by an intense femtosecond near-infrared laser pulse (810 nm) and probed by a weak visible pulse (405 nm). Using a multichannel detection scheme (mass spectra, electron and ion velocity-map imaging), we provide a full disentanglement of the complex dynamics of the vibronically excited parent molecule, its excited ionic states, and fragments. We observed various channels resulting from the strong-field ionization regime. In particular, we observed the formation of the unstable tetracation of fluorene, above-threshold ionization features in the photoelectron spectra, and evidence of ubiquitous secondary fragmentation. We produced a global fit of all observed time-dependent photoelectron and photoion channels. This global fit includes four parent ions extracted from the mass spectra, 15 kinetic-energy-resolved ionic fragments extracted from ion velocity map imaging, and five photoelectron channels obtained from electron velocity map imaging. The fit allowed for the extraction of 60 lifetimes of various metastable photoinduced intermediates.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Electronic structure analysis and DFT benchmarking of Rydberg-type alkali-metal-crown ether, -cryptand, and -adamanzane complexes

Density functional theory (DFT) and electron propagator theory (EPT) calculations were performed to study ground and excited electronic structures of alkali-metal (M) coordinated 9-crown-3, 24-crown-8, [2.1.1]cryptand, o-Me 2 -1.1.1, and 3 6 Adamanzane complexes. Each complex bears an expanded electron in the periphery and occupies diffuse 1p-, 1d-, 1f-type molecular orbitals (or superatomic 1P, 1D, 1F orbitals) in excited electronic states. The calculated superatomic shell model of the M(9-crown-3) 2 is 1S, 1P, 1D, 1F, 2S, 2P, 2D, 1G and it is held by all other complexes up to the studied 1F level. Due to the highly diffuse nature of the electron, the ionization energies of these complexes are significantly lower (1.6–2.0 eV) and hence these complexes belong to the superalkali category. Further, the ab initio EPT ionization energy and the excitation energies of the Li(9-crown-3) 2 were used to evaluate DFT errors associated with a series of exchange correlation functionals that span multiple rungs of Jacob's ladder (i.e., GGA, meta-GGA, global GGA hybrid, meta-GGA hybrid, range-separated hybrid, double-hybrid). Among these, the best performing functional is the range-separated hybrid CAM-B3LYP and the errors are within 6% of high-level ab initio EPT results. The accuracy of CAM-B3LYP is indeed transferable to similar complexes and hence the findings are expected to accelerate the progression of studies of Rydberg-type systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Early-stage oxidation and subsequent damage of the used nuclear fuel extractant TODGA; electron pulse radiolysis and theoretical insights

Radiation induced damage of extractant molecules is a well-known phenomenon responsible for reducing efficiency and increasing the waste and cost of reprocessing used nuclear fuel (UNF). As such, understanding early-stage (pico- to nanoseconds) radiation-induced reaction mechanisms is essential for informing the design of next generation extractants with enhanced radiation robustness. Here, in this work, we utilized picosecond and nanosecond electron pulse radiolysis experiments to probe the early-stage radioactive environment experienced by the organic phase extractant N,N,N',N'-tetraoctyldiglycolamide (TODGA), proposed for separating highly radioactive trivalent minor actinides (specifically americium and curium) from the trivalent lanthanides. Using comparisons to the similar ionization potential (IP) solute p-xylene, this work determined the mechanism of reaction with the ionized diluent (i.e., n-dodecane radical cation, DD˙ + ) is hole transfer to produce TODGA˙ + . At high TODGA concentrations (>100 mM), the majority of this transfer occurs faster than 10 ps via the capture of DD˙ + holes prior to their solvation with a C 37 = 300 mM. The surviving solvated holes were captured with k = (2.38 ± 0.15) × 10 10 M -1 s -1 . Attempts at subsequent hole transfer to lower IP solutes found that only 10% of holes were transferred, indicating bond rupture of TODGA˙ + occurs within 2.6 ns at 200 mM TODGA. Possible reaction pathways for the rapid decomposition of TODGA˙ + were explored using a combination of experiments and density functional theory (DFT) calculations.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2024

Aliphatic Amines from Waste Polyolefins by Tandem Pyrolysis, Hydroformylation, and Reductive Amination

Pyrolysis of waste plastics can produce a product mixture with a high concentration of olefins (>50 wt%). The olefins, as building blocks in the petroleum industry, are potential precursors for valuable commodity chemicals with higher values (>$2000 per ton). In this work, we produce aldehydes by hydroformylation of the olefins present in pyrolysis oil from colored post-consumer recycled high-density polyethylene (PCR-HDPE). The obtained aldehydes in the oil are then converted into aliphatic amines via reductive amination with a Ru/C catalyst. The aminated oil was characterized by multiple analytical chemistry techniques including elemental analysis, nuclear magnetic resonance spectroscopy, high-resolution liquid chromatography-mass spectrometry, and gas chromatography-mass spectrometry with a Polyarc flame ionization detector. The concentration of metals in the PCR-HDPE and oil changes during the tandem processes, showing limited effects of these elements (e.g., Al, Ca, Fe, Mg, Ti, Zn) on hydroformylation and reductive amination. Additionally, we demonstrated that reductive amination of aldehydes with varied carbon numbers and branching properties can be achieved in the presence of a complex mixture, including paraffins and aromatics. The results indicate that waste plastics have the potential to serve as a renewable source for mono and di aliphatic amines, thereby diminishing reliance on fossil feedstocks as the current primary amine source.

aliphatic amines↗
DOE OSTI2024

Radiation-assisted electrochemical reduction of CO 2 to CO

Carbon monoxide (CO) is a versatile intermediate feedstock for many applications and can be produced through the electrochemical reduction of carbon dioxide (CO 2 ). However, current electrochemical CO production is hindered by high overall costs, primarily due to low conversion efficiencies and significant energy requirements. Herein, we report a unique way of enhancing the electrochemical reduction of CO 2 to CO using gamma (γ) photons. The γ-irradiation applied to the electrochemical cell setup induces the production of e˙ - , which results in an increased CO 2 ionization and production of excited CO 2 (CO$^{*}_{2}$) molecules via lower energy barrier. The ionized CO 2 ˙ - is quickly stabilized over a silver catalyst, providing an alternative low activation energy route for CO 2 reduction. In conclusion, a decrease in the overpotential barrier enhanced the electrochemical reduction of CO 2 to CO by 25%.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2024

A neutron fluence map of the Los Alamos National Laboratory Godiva IV critical assembly

A neutron fluence map and a total ionizing dose map of the Los Alamos National Laboratory Godiva IV fast burst critical assembly was generated using passive reactor dosimetry, comprised of sulfur pellets and thermoluminescent dosimeters. Godiva IV is an unmoderated, fast burst, critical assembly constructed of approximately 65 kg of highly enriched uranium fuel alloyed with 1.5 % molybdenum for strength. The mapping was performed during a single 75.6 ºC temperature rise burst operation, with the top and sides of the cylindrical Godiva-IV Top Hat covered in passive dosimetry. Dosimetry was placed in a symmetric pattern around the Top Hat, with higher concentrations near the control rods and burst rod. A specific portion of the lower quadrant of the burst rod was mapped to confirm a testing region where the neutron fluence varied by no more than ± 5%. The results will be used to assess the neutron, gamma, and total ionizing dose environment in three-dimensional space around the assembly for higher fidelity experiment placement, active dosimetry positioning, and radiation field characterization.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗