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At least 325 records · Page 18
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

An excited state dynamics driven reaction: wavelength-dependent photoisomerization quantum yields in [Ru(bpy) 2 (dmso) 2 ] 2+

We report the excited-state behavior of a structurally simple bis -sulfoxide complex, cis -S,S-[Ru(bpy) 2 (dmso) 2 ] 2+ , as investigated by femtosecond pump–probe spectroscopy. The results reveal that a single photon prompts phototriggered isomerization of one or both dmso ligands to yield a mixture of cis -S,O-[Ru(bpy) 2 (dmso) 2 ] 2+ and cis -O,O-[Ru(bpy) 2 (dmso) 2 ] 2+ . The quantum yields of isomerization of each product and relative product distribution are dependent upon the excitation wavelength, with longer wavelengths favoring the double isomerization product, cis -O,O-[Ru(bpy) 2 (dmso) 2 ] 2+ . Transient absorption measurements on cis -O,O-[Ru(bpy) 2 (dmso) 2 ] 2+ do not reveal an excited-state isomerization pathway to produce either the S,O or S,S isomers. Femtosecond pulse shaping experiments reveal no change in the product distribution. Pump–repump–probe transient absorption spectroscopy of cis -S,S-[Ru(bpy) 2 (dmso) 2 ] 2+ shows that a pump–repump time delay of 3 ps dramatically alters the S,O:O,O product ratio; pump–repump–probe transient absorption spectroscopy of cis -O,O-[Ru(bpy) 2 (dmso) 2 ] 2+ with a time delay of 3 ps uncovers an excited-state isomerization pathway to produce the S,O isomer. In conjunction with low-temperature steady-state emission spectroscopy, these results are interpreted in the context of an excited-state bifurcating pathway, in which the isomerization product distribution is determined not by thermodynamics, but rather as a dynamics driven reaction.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Decomposition pathways and mitigation strategies for highly-stable hydroxyphenazine flow battery anolytes

Aqueous organic redox flow batteries are a promising technology for large-scale energy storage. The stability of the redox active organic molecules is increasingly being recognized as one of the major hurdles. Upon extended flow battery cycling, 7,8-dihydroxyphenazine-2 sulfonic acid (DHPS) undergoes desulfonation and reduction of a phenolic C–O bond to yield a mixture of 7/8-hydroxyphenazine-2-sulfonic acid, as well as hydrogenation of the aromatic ring system. Density functional theory (DFT) analysis of the charged DHPS, its ring-hydrogenated products, and variably substituted hydroxy phenazines has led to the development of a series of dihydroxylated phenazine isomers which provide insight into the effects of substitution pattern on solubility and stability. Seven dihydroxyphenazine (DHP) isomers were synthesized and their solubilities, electrochemical properties, flow battery cycling performance, and degradation pathways have been investigated. Based on theoretical and experimental results, hydroxyl substitution at the 1, 4, 6 and 9 positions yields highly stable derivatives, while substitution at the 2, 3, 7, and 8 positions results in unstable derivatives. Flow cells of 1,4- and 1,6-DHPs coupled with ferro/ferricyanide achieved high stabilities, with temporal capacity loss of 0.029 and 0.031% per day, respectively. Decomposition of 1,8- and 2,7-DHPs were found to arise from irreversible hydrogen rearrangement (tautomerization), yielding redox-inactive species. These results provide a detailed understanding of decomposition pathways and mitigation strategies for phenazine-based anolytes, and can provide general design guidelines for the development of stable redox-active organics.

25 ENERGY STORAGE↗
DOE OSTI2022

A combined theoretical and experimental study of small anthracene–water clusters

Water-cluster interactions with polycyclic aromatic hydrocarbons (PAHs) are of paramount interest in many chemical and biological processes. Here we report a study of anthracene monomers and dimers with water (up to four)-cluster systems utilizing molecular beam vacuum-UV photoionization mass spectrometry and density functional calculations. Structural loss in photoionization efficiency curves when adding water indicates that various isomers are generated, while theory indicates only a slight shift in energy in photoionization states of different isomers. Calculations reveal that the energetic tendency of water is to remain clustered and not to disperse around the PAH. Theoretically, we observe water confinement exclusively in the case of four water clusters and only when the anthracenes are in a cross configuration due to optimal OH∙∙∙π interactions, indicating dependence on the size and structure of the PAH. Furthermore theory sheds light on the structural changes that occur in water upon ionization of anthracene, due to the optimal interactions of the resulting hole and water hydrogen atoms.

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

Formation of the C 4 H n + ( n = 2–5) ions upon ionization of acetylene clusters in helium droplets

Infrared (IR) spectroscopy using ultracold helium nanodroplet matrices has proven to be a powerful method to interrogate encapsulated ions, molecules, and clusters. Due to the helium droplets’ high ionization potential, optical transparency, and ability to pick up dopant molecules, the droplets offer a unique modality to probe transient chemical species produced via photo- or electron impact ionization. Here, in this work, helium droplets were doped with acetylene molecules and ionized via electron impact. Ion-molecule reactions within the droplet volume yield larger carbo-cations that were studied via IR laser spectroscopy. This work is focused on cations containing four carbon atoms. The spectra of C 4 H 2 + , C 4 H 3 + , and C 4 H 5 + are dominated by diacetylene, vinylacetylene, and methylcyclopropene cations, respectively, which are the lowest energy isomers. On the other hand, the spectrum of C 4 H 4 + ions hints at the presence of several co-existing isomers, the identity of which remains to be elucidated.

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

Assessment of DFT functionals for a minimal nitrogenase [Fe(SH) 4 H]- model employing state-of-the-art ab initio methods

We have designed a [Fe(SH)4H]- model with the fifth proton binding either to Fe or S. We show that the energy difference between these two isomers (ΔE) is hard to estimate with quantum-mechanical (QM) methods. For example, different density functional theory (DFT) methods give ΔE estimates that vary by almost 140 kJ/mol, mainly depending on the amount of exact Hartree–Fock included (0%–54%). The model is so small that it can be treated by many high-level QM methods, including coupled-cluster (CC) and multiconfigurational perturbation theory approaches. With extrapolated CC series (up to fully connected coupled-cluster calculations with singles, doubles, and triples) and semistochastic heat-bath configuration interaction methods, we obtain results that seem to be converged to full configuration interaction results within 5 kJ/mol. Our best result for ΔE is 101 kJ/mol. With this reference, we show that M06 and B3LYP-D3 give the best results among 35 DFT methods tested for this system. Brueckner doubles coupled cluster with perturbaitve triples seems to be the most accurate coupled-cluster approach with approximate triples. CCSD(T) with Kohn–Sham orbitals gives results within 4–11 kJ/mol of the extrapolated CC results, depending on the DFT method. Single-reference CC calculations seem to be reasonably accurate (giving an error of ~5 kJ/mol compared to multireference methods), even if the D1 diagnostic is quite high (0.25) for one of the two isomers.

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

How generic is iodide-tagging photoelectron spectroscopy: An extended investigation on the Gly· X - (Gly = glycine, X = Cl or Br) complexes

We report a joint negative ion photoelectron spectroscopy (NIPES) and quantum chemical computational study on glycine-chloride/bromide complexes (denoted Gly·X - , X = Cl/Br) in close comparison to the previously studied Gly·I - cluster ion. Combining experimental NIPE spectra and theoretical calculations, various Gly·X - complexes were found to adopt the same types of low-lying isomers, albeit with different relative energies. Despite more congested spectral profiles for Gly·Cl - and Gly·Br - , spectral assignments were accomplished with the guidance of the knowledge learned from Gly·I - , where a larger spin–orbit splitting of iodine afforded well-resolved, recognizable spectral peaks. Three canonical plus one zwitterionic isomer for Gly·Cl - and four canonical conformers for Gly·Br - were experimentally identified and characterized in contrast to the five canonical ones observed for Gly·I - under similar experimental conditions. Taken together, this study investigates both genericity and variations in binding patterns for the complexes composed of glycine and various halides, demonstrating that iodide-tagging is an effective spectroscopic means to unravel diverse ion-molecule binding motifs for cluster anions with congested spectral bands by substituting the respective ion with iodide.

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

High- K , two-quasiparticle states in Gd 160

Excited states in Gd 160 were populated via β decay from the low- and high-spin isomers in Eu 160 . The high-spin, K π = 5 - state feeds several two-quasiparticle levels, as well as a sequence associated with a γ vibration and a K π = 4 + , hexadecapole vibrational structure. The decay scheme was significantly improved with the observation of new transitions and states when compared with the two competing level schemes from over four decades ago. Configuration assignments for some of the multiquasiparticle levels have been suggested, based upon decay properties, systematics from neighboring nuclei, and comparisons with theoretical calculations. Finally, in addition, 15 new low-spin states and approximately 60 new transitions were observed resulting from the decay of the low-spin Eu 160 isomer.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2020

γ-ray measurements in fast-neutron-induced reactions on 203 Tl

Fast-neutron-induced reactions can be used to characterize reaction mechanisms, investigate nuclear structure, and impose constraints on nuclear models. Because of the difficulty in predicting such effects, experimental data are important to constrain models. Thallium isotopes located close to the doubly magic Pb 208 nucleus are important for comparison with shell-model calculations. Study the population of excited states in Tl 203 and lighter isotopes in such reactions. Our methods are as follows. γ -ray cross sections were measured. The data were taken by using the Germanium Array for Neutron-Induced Excitations spectrometer. The pulsed neutron source of the Los Alamos Neutron Science Center's Weapons Neutron Research facility provided neutrons in the energy range from 1 to 300 MeV. The time-of-flight technique was used to determine the incident neutron energies. Cross sections for emission of several γ rays in 20 reaction channels were determined. Candidates for the intruder 9 / 2 - state in Tl 203 , from the odd proton in the h 9 / 2 orbital, and the first 5 + states in Tl 202 , 204 , from admixture of configurations, were identified. The excitation energy of the candidate 9 / 2 - , π h 9 / 2 state is in good agreement with the theoretical prediction from a semi-empirical weak-coupling model and its half-life is in the range of tens of nanoseconds. The feeding of a previously known isomer in Tl 202 exhibits similarities with the feeding of other isomers in this mass region.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2020

Search for Dark Matter Induced Deexcitation of 180 Ta m

Weak-scale dark matter particles, in collisions with nuclei, can mediate transitions between different nuclear energy levels. In particular, owing to sizeable momentum exchange, dark matter particles can enable de-excitation of nuclear isomers that are extremely long lived with respect to regular radioactive decays. In this paper, we utilize data from a past experiment with 180 Ta m to search for γ-lines that would accompany dark matter induced de-excitation of this isomer. Non-observation of such transitions above background yields the first direct constraint on the lifetime of 180 Ta m against DM-initiated transitions: T 1/2 > 1.3 × 10 14 a at 90% C.I. Using this result, we derive novel constraints on dark matter models with strongly interacting relics, and on models with inelastic dark matter particles. Existing constraints are strengthened by this independent new method. As a result, the obtained limits are also valid for the Standard Model γ-decay of 180 Ta m .

150 ≤ A ≤ 189↗
DOE OSTI2020

Properties of 187 Ta Revealed through Isomeric Decay

Mass-separated 187 Ta114 in a high-spin isomeric state has been produced for the first time by multi-nucleon transfer reactions, employing an argon gas stopping cell and laser ionisation. Here, internal $γ$ rays revealed a $T$ 1/2 = 7.3±0.9 s isomer at 1778±1 keV, which decays through a rotational band with perturbations associated with the approach to a prolate-oblate shape transition. Model calculations show less influence from triaxiality compared to heavier elements in the same mass region. The isomer decay reduced $E$2 hindrance factor, $f$ $ν$ = 27±1, supports the interpretation that axial symmetry is approximately conserved.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2024

Laser Excitation of the Th-229 Nucleus

The 8.4 eV nuclear isomer state in Th-229 is resonantly excited in Th-doped CaF 2 crystals using a tabletop tunable laser system. A resonance fluorescence signal is observed in two crystals with different Th-229 dopant concentrations, while it is absent in a control experiment using Th-232. The nuclear resonance for the Th 4 + ions in Th: CaF 2 is measured at the wavelength 148.3821(5) nm, frequency 2020.409(7) THz, and the fluorescence lifetime in the crystal is 630(15) s, corresponding to an isomer half-life of 1740(50) s for a nucleus isolated in vacuum. These results pave the way toward Th-229 nuclear laser spectroscopy and realizing optical nuclear clocks. Published by the American Physical Society 2024

Physics↗
DOE OSTI2025

Seniority Structure in Neutron-Rich Nucleus 128 Ag : Evidence for Robustness of 𝑁 = 82 Shell Closure in Silver Isotopes

The spectroscopic studies of very neutron-rich nucleus 128 Ag have been performed for the first time at the Radioactive Isotope Beam Factory of RIKEN. A new seniority isomer with a half-life of 1.60(7) μs has been identified and is proposed to have a spin-parity of 16 - with a maximally aligned configuration comprising three proton holes in the g 9/2 orbital and one neutron hole in the h 11/2 orbital. The new level structure in 128 Ag is quite well described by shell model calculations without invoking excitations across the Z = 50 and N = 82 shell gaps, and presents a good case of seniority scheme in odd-odd nuclei in the south vicinity of the double-magic nucleus 132 Sn. With a classification of various components of the proton-neutron interaction, the inversion of lowest-lying 9 - and 10 - states between 128 Ag and its neighboring isotone 130 In is found to be dynamically ascribed to the seniority-nonconserving proton-neutron interaction components. The structure above 10 - up to the 16 - isomer in 128 Ag shows remarkable similarities to seniority structures in the semimagic nuclei 128 Pd and 130 Cd. These spectroscopic features in 128 Ag indicate that the N = 82 shell closure is still robust in silver isotopes.

Luo, D. W. [Peking University, Beijing (China); et↗
DOE OSTI2021

Gas Phase Synthesis of Benzene via the Propargyl Radical Self-Reaction

Polycyclic Aromatic Hydrocarbons (PAHs) have been invoked in fundamental molecular mass growth processes in our galaxy. We provide compelling evidence of the formation of the very first ringed aromatic and building block of PAHs - benzene - via the self-recombination of two resonantly stabilized propargyl (C 3 H 3 ) radicals in dilute environments using isomer selective synchrotron-based mass spectrometry coupled to theoretical calculations. Along with benzene, three other structural isomers (1,5-hexadiyne, fulvene, 2-ethynyl-1,3-butadiene) and o-benzyne are detected and their branching ratios quantified experimentally and verified with the aid of computational fluid dynamics and kinetic simulations. Furthermore, these results uncover molecular growth pathways not only in interstellar, circumstellar, and solar systems environments, but also in combustion systems gaining us a better understanding of the hydrocarbon chemistry of our universe.

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

Twin-free, directly synthesized MFI nanosheets with improved thickness uniformity and their use in membrane fabrication

Zeolite nanosheets can be used for the fabrication of low-defect-density, thin, and oriented zeolite separation membranes. However, methods for manipulating their morphology are limited, hindering progress toward improved performance. We report the direct synthesis (i.e., without using exfoliation, etching, or other top-down processing) of thin, flat MFI nanosheets and demonstrate their use as high-performance membranes for xylene isomer separations. Our MFI nanosheets were synthesized using nanosheet fragments as seeds instead of the previously used MFI nanoparticles. The obtained MFI nanosheets exhibit improved thickness uniformity and are free of rotational and MEL intergrowths as shown by transmission electron microscopy (TEM) imaging. The nanosheets can form well-packed nanosheet coatings. Upon gel-free secondary growth, the obtained zeolite MFI membranes show high separation performance for xylene isomers at elevated temperature (e.g., p-xylene flux up to 1.5 × 10 –3 mol m –2 s –1 and p-/o-xylene separation factor of ~600 at 250°C).

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

Dehalogenation of Chlorinated Ethenes to Ethene by a Novel Isolate, “ Candidatus Dehalogenimonas etheniformans”

Dehalococcoides mccartyi strains harboring vinyl chloride (VC) reductive dehalogenase (RDase) genes are keystone bacteria for VC detoxification in groundwater aquifers, and bioremediation monitoring regimens focus on D. mccartyi biomarkers. We isolated a novel anaerobic bacterium, “Candidatus Dehalogenimonas etheniformans” strain GP, capable of respiratory dechlorination of VC to ethene. This bacterium couples formate and hydrogen (H2) oxidation to the reduction of trichloro-ethene (TCE), all dichloroethene (DCE) isomers, and VC with acetate as the carbon source. Cultures that received formate and H2 consumed the two electron donors concomitantly at similar rates. A 16S rRNA gene-targeted quantitative PCR (qPCR) assay measured growth yields of (1.2 ± 0.2) × 10 8 and (1.9 ± 0.2) × 10 8 cells per μmol of VC dechlorinated in cultures with H 2 or formate as electron donor, respectively. About 1.5-fold higher cell numbers were measured with qPCR targeting cerA, a single-copy gene encoding a putative VC RDase. A VC dechlorination rate of 215 ± 40 μmol L -1 day -1 was measured at 30°C, with about 25% of this activity occurring at 15°C. Increasing NaCl concentrations progressively impacted VC dechlorination rates, and dechlorination ceased at 15 g NaCl L -1 . During growth with TCE, all DCE isomers were intermediates. Tetrachloroethene was not dechlorinated and inhibited dechlorination of other chlorinated ethenes. Carbon monoxide formed and accumulated as a metabolic by-product in dechlorinating cultures and impacted reductive dechlorination activity. Finally, the isolation of a new Dehalogenimonas species able to effectively dechlorinate toxic chlorinated ethenes to benign ethene expands our understanding of the reductive dechlorination process, with implications for bioremediation and environmental monitoring.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2020

Improved analysis of arabinoxylan-bound hydroxycinnamate conjugates in grass cell walls

Background: Arabinoxylan in grass cell walls is acylated to varying extents by ferulate and p-coumarate at the 5-hydroxy position of arabinosyl residues branching off the xylan backbone. Some of these hydroxycinnamate units may then become involved in cell wall radical coupling reactions, resulting in ether and other linkages amongst themselves or to monolignols or oligolignols, thereby crosslinking arabinoxylan chains with each other and/or with lignin polymers. This crosslinking is assumed to increase the strength of the cell wall, and impedes the utilization of grass biomass in natural and industrial processes. A method for quantifying the degree of acylation in various grass tissues is, therefore, essential. We sought to reduce the incidence of hydroxycinnamate ester hydrolysis in our recently introduced method by utilizing more anhydrous conditions. Results: The improved methanolysis method minimizes the undesirable ester-cleavage of arabinose from ferulate and p-coumarate esters, and from diferulate dehydrodimers, and produces more methanolysis vs. hydrolysis of xylan-arabinosides, improving the yields of the desired feruloylated and p-coumaroylated methyl arabinosides and their diferulate analogs. Free ferulate and p-coumarate produced by ester-cleavage were reduced by 78% and 68%, respectively, and 21% and 39% more feruloyl and p-coumaroyl methyl arabinosides were detected in the more anhydrous method. The new protocol resulted in an estimated 56% less combined diferulate isomers in which only one acylated arabinosyl unit remained, and 170% more combined diferulate isomers conjugated to two arabinosyl units. Conclusions: Overall, the new protocol for mild acidolysis of grass cell walls is both recovering more ferulate- and p-coumarate-arabinose conjugates from the arabinoxylan and cleaving less of them down to free ferulic acid, p-coumaric acid, and dehydrodiferulates with just one arabinosyl ester. This cleaner method, especially when coupled with the orthogonal method for measuring monolignol hydroxycinnamate conjugates that have been incorporated into lignin, provides an enhanced tool to measure the extent of crosslinking in grass arabinoxylan chains, assisting in identification of useful grasses for biomass applications.

09 BIOMASS FUELS↗
DOE OSTI2023

Reaction nanoscopy of ion emission from sub-wavelength propanediol droplets

Abstract Droplets provide unique opportunities for the investigation of laser-induced surface chemistry. Chemical reactions on the surface of charged droplets are ubiquitous in nature and can provide critical insight into more efficient processes for industrial chemical production. Here, we demonstrate the application of the reaction nanoscopy technique to strong-field ionized nanodroplets of propanediol (PDO). The technique’s sensitivity to the near-field around the droplet allows for the in-situ characterization of the average droplet size and charge. The use of ultrashort laser pulses enables control of the amount of surface charge by the laser intensity. Moreover, we demonstrate the surface chemical sensitivity of reaction nanoscopy by comparing droplets of the isomers 1,2-PDO and 1,3-PDO in their ion emission and fragmentation channels. Referencing the ion yields to gas-phase data, we find an enhanced production of methyl cations from droplets of the 1,2-PDO isomer. Density functional theory simulations support that this enhancement is due to the alignment of 1,2-PDO molecules on the surface. The results pave the way towards spatio-temporal observations of charge dynamics and surface reactions on droplets.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2020

Shock tube and laser absorption study of CO time-histories during combustion of branched alkenes

Combustion experiments of the three isomers of methyl butene compound - 2-methyl-1-butene (2M1B), 2-methyl-2-butene (2M2B), and 3-methyl-1-butene (3M1B), have been carried out in a shock tube using laser absorption technique. Carbon monoxide (CO) time-histories are obtained behind reflected shockwaves over the temperature range of 1350–1630 K near 9.3 atm with stoichiometric mixtures of 0.075% fuel in O2/Ar. Comparative study of CO time-histories reveals different rates of CO formation indicating different ignition delay time of the methyl butene isomers.

09 BIOMASS FUELS↗