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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 55 records · Page 3
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Photo-induced structural dynamics of o -nitrophenol by ultrafast electron diffraction

The photo-induced dynamics of o-nitrophenol, particularly its photolysis, has garnered significant scientific interest as a potential source of nitrous acid in the atmosphere. Although the photolysis products and preceding photo-induced electronic structure dynamics have been investigated extensively, the nuclear dynamics accompanying the non-radiative relaxation of o-nitrophenol on the ultrafast timescale, which include an intramolecular proton transfer step, have not been experimentally resolved. Herein, we present a direct observation of the ultrafast nuclear motions mediating photo-relaxation using ultrafast electron diffraction. Here, this work spatiotemporally resolves the loss of planarity which enables access to a conical intersection between the first excited state and the ground state after the proton transfer step, on the femtosecond timescale and with sub-Angstrom resolution. Our observations, supported by ab initio multiple spawning simulations, provide new insights into the proton transfer mediated relaxation mechanism in o-nitrophenol.

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

Cations impact radical reaction dynamics in concentrated multicomponent aqueous solutions

Ultraviolet (UV) photolysis of nitrite ions (NO 2 – ) in aqueous solutions produces a suite of radicals, viz., NO · , O – , · OH, and · NO 2 . The O – and NO · radicals are initially formed from the dissociation of photoexcited NO 2 – . The O – radical undergoes reversible proton transfer with water to generate · OH. Both · OH and O – oxidize the NO 2 – to · NO 2 radicals. The reactions of · OH occur at solution diffusion limits, which are influenced by the nature of the dissolved cations and anions. Here, we systematically varied the alkali metal cation, spanning the range from strongly to weakly hydrating ions, and measured the production of NO · , · OH, and · NO 2 radicals during UV photolysis of alkaline nitrite solutions using electron paramagnetic resonance spectroscopy with nitromethane spin trapping. Comparing the data for the different alkali cations revealed that the nature of the cation had a significant effect on production of all three radical species. Radical production was inhibited in solutions with high charge density cations, e.g., lithium, and promoted in solutions containing low charge density cations, e.g., cesium. Through complementary investigations with multinuclear single pulse direct excitation nuclear magnetic resonance (NMR) spectroscopy and pulsed field gradient NMR diffusometry, cation-controlled solution structures and extent of NO 2 – solvation were determined to alter the initial yields of · NO and · OH radicals as well as alter the reactivity of NO 2 – toward · OH, impacting the production of · NO 2 . The implications of these results for the retrieval and processing of low-water, highly alkaline solutions that comprise legacy radioactive waste are discussed.

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

Characterizing the multi-dimensional reaction dynamics of dihalomethanes using XUV-induced Coulomb explosion imaging

Site-selective probing of iodine 4d orbitals at 13.1 nm was used to characterize the photolysis of CH 2 I 2 and CH 2 BrI initiated at 202.5 nm. Time-dependent fragment ion momenta were recorded using Coulomb explosion imaging mass spectrometry and used to determine the structural dynamics of the dissociating molecules. Correlations between these fragment momenta, as well as the onset times of electron transfer reactions between them, indicate that each molecule can undergo neutral three-body photolysis. For CH 2 I 2 , the structural evolution of the neutral molecule was simultaneously characterized along the C–I and I–C–I coordinates, demonstrating the sensitivity of these measurements to nuclear motion along multiple degrees of freedom.

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

A comprehensive study on three typical photoacid generators using photoelectron spectroscopy and ab initio calculations

Conducting a comprehensive molecular-level evaluation of a photoacid generator (PAG) and its subsequent impact on lithography performance can facilitate the rational design of a promising 193 nm photoresist tailored to specific requirements. In this study, we integrated spectroscopy and computational techniques to meticulously investigate the pivotal factors of three prototypical PAG anions, p-toluenesulfonate (pTS - ), 2-(trifluoromethyl)benzene-1-sulfonate (TFMBS - ), and triflate (TF - ), in the lithography process. Our findings reveal a significant redshift in the absorption spectra caused by specific PAG anions, attributed to their involvement in electronic transition processes, thereby enhancing the transparency of the standard PAG cation, triphenylsulfonium (TPS + ), particularly at ~193 nm. Furthermore, the electronic stability of PAG anions can be enhanced by solvent effects with varying degrees of strength. Here we observed the lowest vertical detachment energy of 6.6 eV of pTS - in PGMEA solution based on the polarizable continuum model, which prevents anion loss at 193 nm lithography. In addition, our findings indicate gas-phase proton affinity values of 316.4 kcal/mol for pTS - , 308.1 kcal/mol for TFMBS - , and 303.2 kcal/mol for TF - , which suggest the increasing acidity strength, yet even the weakest acid pTS - is still stronger than strong acid HBr. The photolysis of TPS + -based PAG, TPS + ·pTS - , generated an excited state leading to homolysis bond cleavage with the lowest reaction energy of 83 kcal/mol. Overall, the PAG anion pTS - displayed moderate acidity, possessed the lowest photolysis reaction energy, and demonstrated an appropriate redshift. These properties collectively render it a promising candidate for an effective acid producer.

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

Electronic Absorption Spectroscopy and Photochemistry of Criegee Intermediates

Interest in Criegee intermediates (CIs), often termed carbonyl oxides, and their role in tropospheric chemistry has grown massively since the demonstration of laboratory-based routes to their formation and characterization in the gas phase. This article reviews current knowledge regarding the electronic spectroscopy of atmospherically relevant CIs like CH 2 OO, CH 3 CHOO, (CH 3 ) 2 COO and larger CIs like methyl vinyl ketone oxide and methacrolein oxide that are formed in the ozonolysis of isoprene, and of selected conjugated carbene-derived CIs of interest in the synthetic chemistry community. Of the aforementioned atmospherically relevant CIs, all except CH 2 OO and (CH 3 ) 2 COO exist in different conformers which, under tropospheric conditions, can display strikingly different thermal loss rates via unimolecular and bimolecular processes. Calculated photolysis rates based on their absorption properties suggest that solar photolysis will rarely be a significant contributor to the total loss rate for any CI under tropospheric conditions. Nonetheless, there is ever-growing interest in the absorption cross sections and primary photochemistry of CIs following excitation to the strongly absorbing 1 ππ* state, and how this varies with CI, with conformer and with excitation wavelength. Furthermore, the later part of this review surveys the photochemical data reported to date, including a range of studies that demonstrate prompt photo-induced fission of the terminal O–O bond, and speculates about possible alternate decay processes that could occur following non-adiabatic coupling to, and dissociation from, highly internally excited levels of the electronic ground state of a CI.

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

Thermal and photoinduced chemistry of the aromatic Criegee intermediate, benzaldehyde oxide: Implications for indoor air quality

Essential oils contain a complex mixture of volatile organic compounds, ranging from terpenes to aromatics. When released into the indoor air environment or into the atmosphere, they may undergo oxidation to generate complex reactive intermediates that affect indoor air quality. Cinnamaldehyde is one such aromatic molecule that is abundant in essential oils. When released into the indoor air environment, it may undergo oxidation to form a carbonyl oxide (Criegee intermediate) with an aromatic substituent: benzaldehyde oxide. In this manuscript, we present a high-level quantum chemical study that shows that, unlike smaller atmospherically relevant Criegee intermediates, benzaldehyde oxide is expected to undergo solar photolysis on timescales that are competitive with its ground state unimolecular and bimolecular chemistry. We show that aromatic substitution leads to a drastic bathochromic shift in the spectroscopically relevant excited states, revealing that photolysis in the indoor or outdoor environment should not be neglected when modeling the climate and air quality implications of Criegee intermediates with extended conjugation. Here, we predict a range of products that may be important for forming lower volatility compounds via tropospherically relevant photochemistry. To motivate future experimental validation of our results, we propose a viable synthetic procedure of the relevant precursor for generating and stabilizing benzaldehyde oxide.

atmospheric photochemistry↗
DOE OSTI2025

Direct Measurements of Dimethyl Sulfide Oxidation Chemistry: Uncovering the Primary Pathways from Gas Phase to Sulfate Aerosols

We report experimental measurements of dimethyl sulfide oxidation, focusing on a major chemical intermediate, hydroperoxymethyl thioformate (HPMTF). The (photo)chemistry and transport properties of HPMTF, which are critical to accurate modeling of tropospheric sulfur, are not known, partly because current analytical methods are not optimized for elusive chemical intermediates. We investigated dimethyl sulfide oxidation using a custom time-resolved photoionization mass spectrometer, interfaced with pulsed laser photolysis, continuous photolysis, and liquid droplet reactors. We detected and characterized HPMTF (along with other reaction intermediates), quantified its yield, and measured its formation rate coefficient. We also developed a clean, intense, online HPMTF source, suitable for further experimental investigations. Lastly, we measured the mass accommodation coefficient of HPMTF on water droplets – a critical quantity for modeling its atmospheric partitioning between the gas and condensed phases. The experimental platform we developed here enables the exploration of other critical elusive reaction intermediates.

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

Biomass burning and marine aerosol processing over the southeast Atlantic Ocean: a TEM single-particle analysis

This study characterizes single-particle aerosol composition from filters collected during the ObseRvations of Aerosols above CLouds and their intEractionS (ORACLES) and CLoud–Aerosol–Radiation Interaction and Forcing: Year 2017 (CLARIFY-2017) campaigns. In particular the study describes aged biomass burning aerosol (BBA), its interaction with the marine boundary layer and the influence of biomass burning (BB) air on marine aerosol. The study finds evidence of BBA influenced by marine boundary layer processing as well as sea salt influenced by BB air. Secondary chloride aerosols were observed in clean marine air as well as in BB-influenced air in the free troposphere. Higher-volatility organic aerosol appears to be associated with increased age of biomass burning plumes, and photolysis or oxidation may be a mechanism for the apparent increased volatility. Aqueous processing and interaction with the marine boundary layer air may be a mechanism for the presence of sodium on many aged potassium salts. By number, biomass burning potassium salts and modified sea salts are the most observed particles on filter samples. The most commonly observed BC coatings are inorganic salts. These results suggest that atmospheric processes such as photolysis, oxidation and cloud processing are key drivers in the elemental composition and morphology of aged BBA. Fresh BBA inorganic salt content, as it has an important role in the particles' ability to uptake water, may be a key driver in how aqueous processing and atmospheric aging proceed.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2020

Implications of Abiotic Oxygen Buildup for Earth-like Complex Life

One of the chief paradoxes of molecular oxygen (O{sub 2}) is that it is an essential requirement for multicellular eukaryotes on Earth while simultaneously posing a threat to their survival via the formation of reactive oxygen species. In this paper, the constraints imposed by O{sub 2} on Earth-like complex life are invoked to explore whether worlds with abiotic O{sub 2} inventories can harbor such organisms. By taking the major O{sub 2} sources and sinks of Earth-like planets into account using a simple model, it is suggested that worlds that receive time-averaged X-ray and extreme ultraviolet fluxes that are ≳10 times higher than Earth might not be capable of hosting complex lifeforms because the photolysis of molecules such as water may lead to significant O{sub 2} buildup. Methods for testing this hypothesis by searching for anticorrelations between biosignatures and indicators of abiotic O{sub 2} atmospheres are described. In the event, however, that life successfully adapts to high-oxygen environments, these worlds could permit the evolution of large and complex organisms.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2020

High-resolution Spectral Discriminants of Ocean Loss for M-dwarf Terrestrial Exoplanets

In the near future, extremely large ground-based telescopes may conduct some of the first searches for life beyond the solar system. High spectral resolution observations of reflected light from nearby exoplanetary atmospheres could be used to search for the biosignature oxygen. However, while Earth’s abundant O{sub 2} is photosynthetic, early ocean loss may also produce high atmospheric O{sub 2} via water vapor photolysis and subsequent hydrogen escape. To explore how to use spectra to discriminate between these two oxygen sources, we generate high-resolution line-by-line synthetic spectra of both a habitable Earth-like and post-ocean-loss Proxima Centauri b. We examine the strength and profile of four bands of O{sub 2} from 0.63 to 1.27 μm, and quantify their relative detectability. We find that 10 bar O{sub 2} post-ocean-loss atmospheres have strong suppression of oxygen bands, and especially the 1.27 μum band. This suppression is due to additional strong, broad O{sub 2}–O{sub 2} collisionally induced absorption (CIA) generated in these more massive O{sub 2} atmospheres, which is not present for the smaller amounts of oxygen generated by photosynthesis. Consequently, any detection of the 1.27 μm band in reflected light indicates lower Earth-like O{sub 2} levels, which suggests a likely photosynthetic origin. However, the 0.69 μm O{sub 2} band is relatively unaffected by O{sub 2}–O{sub 2} CIA, and the presence of an ocean-loss high-O{sub 2} atmosphere could be inferred via detection of a strong 0.69 μm O{sub 2} band, and a weaker or undetected 1.27 μm band. These results provide a strategy for observing and interpreting O{sub 2} in exoplanet atmospheres, that could be considered by future ground-based telescopes.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2023

Trace Gases, Meteorological Parameters, and GPS data for TRACER-MAP

This dataset includes trace gas, meteorological, and GPS measurements made on Mobile Air Quality Laboratory 2 (MAQL2) for the TRACER-MAP sampling campaign. Trace gas measurements include nitric oxide (NO), nitrogen dioxide (NO2), reactive nitrogen compounds (NOy), ozone (O3), sulfur dioxide (SO2), and carbon monoxide (CO). All trace gases are in units of ppbv, excluding CO which is in ppmv. The dataset also includes the photolysis rate of NO2 (jNO2), latitude and longitude, wind speed (WS), wind direction (WD), ambient relative humidity (RH), ambient pressure (press), and ambient temperature (temp). Units for trace gases are in parts per billion (ppbv), latitude and longitude are in decimal degrees (dd), jNO2 is in per second (per sec), pressure is in millibar (mbar), relative humidity is in percent, the temperature is in degrees C, wind direction is in degrees, and wind speed is in meters per second. All data is 5 minutes averaged.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2020

Conventional and Next Generation Treatment Technologies for PFAS - 20067

In 2016, the United States Environmental Protection Agency (USEPA) established a Health Advisory Limit (HAL) for perfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS) (individually and the summation) of 70 nanograms per liter (ng/L) based on developing toxicological information. These two compounds are among several thousand per- and polyfluoroalkyl substances (PFAS). Due to a multitude of commercially beneficial physical and chemical properties, the availability of PFAS-relevant and practical water treatment technologies is limited. The use of conventional adsorbents, such as activated carbon (AC) and anion exchange (AIX) resins, have become a 'de facto' interim measure to immediately address drinking water above this criterion. However, these adsorbents can have marginal long-term efficiency and are relatively unproven against the diversity of polyfluorinated compounds. Additionally, geochemical and/or co-contaminant competition can significantly impede adsorption based PFAS removal. These challenges may be addressed using engineered filtration, such as reverse osmosis or nanofiltration (RO/NF); however, for larger flow systems RO/NF may have unacceptable reject ratios as high as 35% and the capital cost may preclude these technologies. Extending these technologies to natural waters, which have various degrees of geochemical and co-contaminant competition, often requires a treatment train, combining conventional adsorbents or engineered filtration with pretreatment and more innovative and emerging remediation solutions for PFAS. Conventional and Next Generation water treatment technologies for PFAS generally employ one of three mechanisms (adsorption, separation, or destruction). These mechanisms include many types of technologies for both municipal drinking water and extracted natural water applications. The previously mentioned AC, AIX, and RO/NF are commercially available technologies that are actively being deployed for PFAS treatment. Research and development around these technologies is focused on optimization, and ultimate destruction of PFAS is achieved through incineration. Next Generation water treatment technologies include PFAS-specific flocculants, foam fractionation, novel AIX resins, new engineered adsorptive media, electrochemical treatment, sonolysis, and photolysis, radiation, and plasma (forms of advanced reductive processes [ARP]). Research and development around these technologies is focused on proof of concept and assimilation to real world applications. As the PFAS-relevant destructive technologies (such as incineration, electrochemical treatment, sonolysis, and ARP) are energy intensive, the state of the practice for PFAS water treatment is to focus adsorption/separation based technologies on reducing and concentrating the volume of water requiring destructive treatment. This enables more flexibility with respect to circulation frequency, residence time, and more control over energy usage. Water treatment for PFAS presently requires multiple technologies (i.e. a treatment train) to protect human health in a cost-conscious manner. An investment in research and development to explore new technologies is part of a key initiative for efficient protection of human health. This presentation attempts to review PFAS-relevant water treatment technologies and provide perspective as to their status with respect to applicability and commercial relevance. (authors)

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2022

Copper Complexes with Diazoolefin Ligands and their Photochemical Conversion into Alkenylidene Complexes

Abstract Homometallic copper complexes with alkenylidene ligands are discussed as intermediates in catalysis but the isolation of such complexes has remained elusive. Herein, we report the structural characterization of copper complexes with bridging and terminal alkenylidene ligands. The compounds were obtained by irradiation of Cu I complexes with N‐heterocyclic diazoolefin ligands. The complex with a terminal alkenylidene ligand required isolation in a crystalline matrix, and its structural characterization was enabled by in crystallo photolysis at low temperature.

Kooij, Bastiaan↗
DOE OSTI2022

Copper Complexes with Diazoolefin Ligands and their Photochemical Conversion into Alkenylidene Complexes

Homometallic copper complexes with alkenylidene ligands are discussed as intermediates in catalysis but the isolation of such complexes has remained elusive. Herein, we report the structural characterization of copper complexes with bridging and terminal alkenylidene ligands. The compounds were obtained by irradiation of CuI complexes with N-heterocyclic diazoolefin ligands. Furthermore, the complex with a terminal alkenylidene ligand required isolation in a crystalline matrix, and its structural characterization was enabled by in crystallo photolysis at low temperature.

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

Direct Experimental Observation of the Tetrabromine Cluster Br 4 by Synchrotron Photoionization Mass Spectrometry

We present a first spectroscopic characterization of the homoatomic polyhalogen tetrabromine, Br 4 , in the gas phase. Photolysis of CHBr 3 at 248 nm is used to generate atomic bromine radicals in a flow tube reactor. Resulting combination products are detected by photoionization mass spectrometry at the Advanced Light Source of the Lawrence Berkeley National Laboratory. Interpretation of the experimental mass spectra is informed by calculated adiabatic ionization energies carried out at the CCSD(T)/aug-cc-pVTZ//M06-2X/aug-cc-pVTZ and CCSD(T)/aug-cc-pVTZ//cam-B3LYP/6-311++g** levels of theory. Tunable VUV synchrotron radiation enables the collection of the mass-selected photoionization spectra by which Br 4 is assigned using Franck-Condon simulations of a Br 2 dimer with a stretched tetrahedral geometry.

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

Iron-activated persulfate oxidation degrades aqueous Perfluorooctanoic acid (PFOA) at ambient temperature

Perfluorooctanoic acid (PFOA, C 8 HF 15 O 2 ) is an industrial surfactant that is highly resistant to natural breakdown processes such as those mediated by heat, hydrolysis, photolysis, and biodegradation. Many efforts have been developed to breakdown PFOA to less harmful species due to its widespread human exposure and potential toxicity. However, these methods require high temperature or specialized equipment with serious disadvantages of high energy cost for long-term use. For this paper, we investigated the effectiveness of PFOA degradation by ferrous iron-activated persulfate oxidation (IAPO) under various aqueous geochemical conditions. Approximately 64% of PFOA (initial concentration = 1.64 μmol L –1 ) was degraded after 4 h under illuminated anoxic conditions at ambient temperature. This degradation rate and magnitude support the potential use of IAPO as a novel inexpensive and environmentally friendly method to remediate PFOA in soil and groundwater.

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

Reactions of hydrazine with the amidogen radical and atomic hydrogen

The rate coefficient k 1 for NH 2 + N 2 H 4 was measured to be (5.4 ± 0.4) × 10 –14 cm 3 molecule –1 s –1 at 296 K. NH 2 was generated by pulsed laser photolysis of NH 3 at 193 nm, and monitored as a function of time by pulsed laser-induced fluorescence excited at 570.3 nm under pseudo-first order conditions in the presence of excess N 2 H 4 in an Ar bath gas. This reaction was also investigated computationally, with geometries and scaled frequencies obtained with M06-2X/6-311+G(2df,2p) theory, and single-point energies from CCSD(T)-F12b/cc-pVTZ-F12 theory, plus a term to correct approximately for electron correlation through CCSDT(Q). Three connected transition states are involved and rate constants were obtained via Multistructural Improved Canonical Variational Transition State Theory with Small Curvature Tunneling. Combination of experiment and theory leads to a recommended rate coefficient for hydrogen abstraction of k 1 = 6.3 × 10 –23 T 3.44 exp(+289 K/T) cm 3 molecule –1 s –1 . The minor channel for H + N 2 H 4 forming NH 2 + NH 3 was characterized computationally as well, to yield 5.0 × 10 –19 T 2.07 exp(-4032 K/T) cm 3 molecule –1 s –1 . Finally, these results are compared to several discordant prior estimates, and are employed in an overall mechanism to compare with measurements of half-lives of hydrazine in a shock tube.

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

Photochemical reactions on aerosols at West Antarctica: A molecular case-study of nitrate formation among sea salt aerosols

Environmental implications of climate change are complex and exhibit regional variations both within and between the polar regions. The increase of solar UV radiation flux over Antarctica due to stratospheric ozone depletion creates the optimal conditions for photochemical reactions on the snow. Modeling, laboratory, and indirect field studies suggest that snowpack process release gases to the atmosphere that can react on sea salt particles in remote regions such as Antarctica, modifying aerosol composition and physical properties of aerosols. Here, we present evidence of photochemical processing in West Antarctica aerosols using microscopic and chemical speciation of individual atmospheric particles. Individual aerosol particles collected at the Brazilian module Criosfera 1 were analyzed by scanning transmission X-ray microscopy with near edge X-ray absorption fine structure spectroscopy (STXM/NEXAFS) combined with computer controlled scanning electron microscopy (CCSEM) with energy-dispersive X-ray (EDX) microanalysis. The displacement of chlorine relative to sodium was observed over most of the sea salt particles. Particles with a chemical composition consistent with NaCl-NO3 contributed up to 30% of atmospheric particles investigated. Overall, this study provides evidence that the snowpack and particulate nitrate photolysis should be considered in dynamic partition equilibrium in the troposphere. Finally, these findings may assist in reducing modeling uncertainties and present new insights into the aerosol chemical composition in the polar environment.

54 ENVIRONMENTAL SCIENCES↗