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DOE OSTI2022

Modifying Frank–Kasper Mesophases by Modulating Chain Configuration in PDMS- b -PTFEA Copolymers

The common spherical mesophases observed from chemically distinct compounds have promoted extensive studies of packing structures in soft-matter self-assemblies. In this report we present a new approach for controlling sphere-packing phases by modulating homologous copolymer chain configurations. To this end, three sets of sample pairs, compositionally asymmetric polydimethylsiloxane-b-poly(2,2,2-trifluoroethyl acrylate) (PDMS-b-PTFEA) diblock copolymers (diBCPs) and their homologues containing the corresponding triblock copolymer (triBCP), are synthesized via atom transfer radical polymerization and designed with the consistent volume fractions of the core-forming PTFEA block, f PTFEA = 0.20, 0.18, and 0.15. We identify the formation of C15 and hexagonally close-packed (HCP) phases in the triBCP-containing PDMS-b-PTFEAs, whereas the sigma and C14 phases are formed in their diBCP analogues, respectively. These phase shifts into C15 and HCP, due to molecular configuration differences, reveal a significant yet unrealized role of chain configurations and the associated chain size effects in determining the stable sphere-packing phases in BCP systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA NTRS1994

Measurement of atmospheric OH by titration of near-IR fluorescent dyes

Recent research has shown that certain polymethine dyes can be detected at ultratrace levels (greater than or equal to 6x10(exp -14) M) in solution by fluorimetry. These detection limits are possible because of the inherent sensitivity of fluorescence techniques, because the dyes fluoresce in the near infrared region where background interference is negligible, and because powerful infrared diode lasers are now available to improve the signal to noise ratio. Other work has shown that the hydroxyl radical destroys the ability of polymethine dyes to fluoresce. These observations form the basis for a new hydroxyl radical detector that is essentially a fluorometric titrator. Theoretically, the detector should show an acceptable sensitivity and response time. Assuming that the atmospheric HO concentration is about 10(exp -11) moles m(exp -3) (i.e. 10(exp 6) molecules cm(exp -3)), then 10 L of air 'titrated' with 20 mL of 10(exp -11) M dye solution (an easily detected concentration) should result in a drop in the fluorescent signal of 50 percent - a readily detectable change. At a flow rate of 3 L min(exp -1) the sampling time would be 3 minutes. The biggest potential problem is selectivity: other oxidants may also cause the fluorescence signal to be lost. The chemistry of polymethine dyes has not been studied in detail and so no quantitative data are available. However, a survey of the literature suggests that in general HO should react up to six orders of magnitude faster than HO2 and other radicals such as RO2 and RO. It should also react much more rapidly than H2O2 and O3. Thus it may be possible to discriminate kinetically against potential interfering substances. It was shown in the laboratory that 10(exp -4) M H2O2 has little effect on the absorption spectrum of the dye IR125 over a period of hours but that the band at 780 nm is slowly lost in water over a period of days even under argon in the dark. By contrast, DMSO solutions of IR125 are stable.

Betterton, Eric A.↗

DOE OSTI2020

Rare-Earth Metal Tetrathiafulvalene Carboxylate Frameworks as Redox-Switchable Single-Molecule Magnets

Not provided.

Chemistry↗

DOE OSTI2021

Isolated [B 2 (CN) 6 ] 2– : Small Yet Exceptionally Stable Nonmetal Dianion

Here, we report the observation of a small, yet remarkably stable, metal-free hexacyanodiborate dianion [B 2 (CN) 6 ] 2– in the gas phase. Negative ion photoelectron spectroscopy (NIPES) was employed to measure its spectra at multiple laser wavelengths, yielding a 1.9 eV electron binding energy (EBE) —a remarkably high value of electronic stability and a ~2.60 eV repulsive Coulomb barrier (RCB) for electron detachment. This rationalizes the observation of this dianion, although homolytic charge-separation dissociation into two [B(CN) 3 ] •– is energetically favorable. Quantum chemical calculations demonstrate a $D_{3d}$ staggered conformation for both the dianion and radical monoanion, and the calculated EBE and RCB match the experimental values well. The simulated density of states spectrum reproduces all measured electronic transitions, while the simulated vibrational progressions for the ground state transition cover a much narrower EBE range compared to the experimental band, indicating appreciable auto-photodetachment via electronically excited dianion resonances

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2022

First-principles study of the T center in silicon

The T center in silicon is a well-known carbon-based color center that has been recently considered for quantum technology applications. Using first-principles computations, we show that the excited state is formed by a defect-bound exciton made of a localized defect state occupied by an electron to which a hole is bound. The localized state is of strong carbon p character and reminiscent of the localization of the unpaired electron in the ethyl radical molecule. The radiative lifetime for the defect-bound exciton is calculated to be on the order of microseconds, much longer than for other quantum defects such as the nitrogen vacancy center in diamond and in agreement with experiments. The longer lifetime is associated with the small transition dipole moment as a result of the very different nature of the localized and delocalized states forming the defect-bound exciton. Finally, we use first-principles calculations to assess the stability of the T center. Here, we find the T center to be stable against decomposition into simpler defects when keeping the stoichiometry fixed. However, we identify that the T center is easily prone to (de)hydrogenation and so requires very precise annealing conditions (temperature and atmosphere) to be efficiently formed.

36 MATERIALS SCIENCE↗

NASA NTRS2003

[13C]-Specific labeling of 8-2' linked (-)-cis-blechnic, (-)-trans-blechnic and (-)-brainic acids in the fern Blechnum spicant

In vivo administration experiments using stable (13C) and radio (14C) labeled precursors established that the optically active 8-2' linked lignans, (-)-cis-blechnic, (-)-trans-blechnic and (-)-trans-brainic acids, were directly derived from L-phenylalanine, cinnamate, and p-coumarate but not either from tyrosine or acetate. The radiochemical time course data suggest that the initial coupling product is (-)-cis-blechnic acid, which is then apparently converted into both (-)-trans-blechnic and (-)-trans-brainic acids in vivo. These findings provide additional evidence for vascular plant proteins engendering distinct but specific phenolic radical-radical coupling modes, i.e., for full control over phenylpropanoid coupling in vivo, whether stereoselective or regiospecific.

NASA Discipline Plant Biology↗

DOE OSTI2025

Electrons and Their Multiple Kinetic Fates in an Ionic Liquid

Ionic liquids (ILs) for electrochemical, nuclear, and solar energy applications operate under harsh conditions, where electrons and transient radical species can form. This communication discusses why anions such as bis(trifluoromethylsulfonyl)imide (Tf 2 N − ) are reduced at the electron-rich electrode whereas in laser photoionization or pulse radiolysis studies, where electrons are ejected from species in the bulk, we often detect long-lived electrons in cavities that interact with IL cations instead. This work argues that bulk excess electrons generated photolytically or radiolytically follow kinetically favored pathways. As such, cavity electrons may not be the most energetically favorable states, but when they form, and they do form, they are kinetically stable. Reduction reactions of anions or electron localization in cavities and subsequent reactions are all expected outcomes. Here we focus on a pyrrolidinium-based IL of the dicyanamide (N(CN) 2 − ) anion because of its large electrochemical window and very low viscosity, which are ideal for energy applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2024

High-Speed OH-PLIF Diagnostics of Flame Flashback in Low Swirl Hydrogen-Enriched Flames

Hydrogen-enrichment is a potential strategy to reduce carbon emissions for the development of next-generation lean premixed combustors. However, the higher flashback propensity with hydrogen enrichment owing to the faster chemical kinetics is one of the key challenges in existing natural gas turbine combustors. The fundamentals of stabilized flame dynamics and flashback events in a premixed low swirl burner (LSB) configuration are visualized experimentally using nanosecond (ns)-based high-speed hydroxyl radical planar laser-induced fluorescence (OH-PLIF). Swirlers with two different turning angles, 26 and 33 and three different center-body hole diameters, 1.08, 1.12 and 1.16 mm with measured swirl numbers varying from 0.43 to 0.49 are tested in this study at atmospheric temperature and pressure inlet conditions. The inlet conditions are varied systematically with respect to pre-mixer velocities (V), flame equivalence ratio (ϕ) and hydrogen content (X_(H_2 )) for 50%-90% (H2, by mole) H2/ CH4 reactant mixtures and OH-PLIF characterization is performed in a stable flame at 20 kHz repetition rate. An increase in flashback propensity is observed with increasing ϕ, X_(H_2 ) and decreasing V via detailed investigation of flame lift-off length (L) above the burner rim.

Parajuli, Pradeep↗

NASA NTRS2000

Methanogenesis, Mesospheric Clouds, and Global Habitability

Hyperthermophilic methanogens can exist in a deep hot biosphere up to 110 C, or 10 km deep. Methane (CH4) itself is thermodynamically stable to depths of 300 km. Geologic (microbial plus abiogenic thermal) methane is transported upward, attested to by its association with helium, to form petroleum pools. Near or at the surface, geologic CH4 mixes with other natural and with anthropogenic CH4 yielding annual emissions into the atmosphere of 500 Tg, of which 200 Tg are natural and 300 Tg are man-made. The atmospheric lifetime of CH4, a greenhouse gas 20 times more effective than CO2 in raising global temperatures, is approximately 10 years. It is removed from the atmosphere mainly by reactions with hydroxyl radical (OH) to form CO2, but also by dry soil and by conversion to H2O in the stratosphere and middle atmosphere. A sudden rise in atmospheric temperatures by 9-12 C some 55 million years ago has been explained by the release in a few thousand years of three trillion tons of CH4 out of 15 trillion tons that had formed beneath the sea floor. What prevented this CH4-induced greenhouse effect from running away? An analog to the CH4-burp of 55 million years ago is the CH4-doubling over the past century which resulted in a increase in upper level H2O from 4.3 ppmv to 6 ppmv. This 30% increase in H2O vapor yielded a tenfold increase in brightness of polar mesospheric clouds because of a strong dependence of the ice particle nucleation rate on the water saturation ratios. Models show that at a given temperature the optical depth of mesospheric clouds scales as [H2O]beta with beta varying between 4 and 8. Radiative transfer tools applied to mesospheric particles suggest that an optical depth of approximately one, or 1000 times the current mesospheric cloud optical depth, would result in tropospheric cooling of about 10 K. Assuming beta=6, a thousandfold increase in optical thickness would require a three-fold increase of H2O, or a 20-fold increase of CH4. At the current rate of anthropogenic emissions this is expected to occur within the next 1000 years. This timescale is also commensurate with what has been assumed for the CH4- burp 55 million years ago.

Pueschel, Rudolf F.↗

DOE OSTI2022

Thermally stable hydrocarbon-based anion exchange membrane and ionomers

An anion exchange membrane is composed of a copolymer of 1,1-diphenylethylene and one or more styrene monomers, such as 4-tert-butylstyrene. The copolymer includes a backbone substituted with a plurality of ionic groups coupled to phenyl groups on the backbone via hydrocarbyl tethers between about 1 and about 7 carbons in length. High-temperature conditions enabled by these copolymers enhance conductivity performance, making them particularly suitable for use in anion exchange membranes in fuel cells, electrolyzers employing hydrogen, ion separations, etc. The properties of the membranes can be tuned via the degree of functionalization of the phenyl groups and selection of the functional groups, such as quaternary ammonium groups. Several processes can be used to incorporate the desired ionic functional groups into the polymers, such as chloromethylation, radical bromination, Friedel-Crafts acylation and alkylation, sulfonation followed by amination, or combinations thereof.

Lee, Sangwoo↗

DOE OSTI2024

Thermally stable hydrocarbon-based anion exchange membrane and ionomers

Lee, Sangwoo↗

DOE OSTI2024

Iron( IV ) alkyl complexes: electronic structure contributions to Fe–C bond homolysis and migration reactions that form N–C bonds from N 2

High-valent iron alkyl complexes are rare, as they are prone to Fe–C bond homolysis. Here, we describe an unusual way to access formally iron(IV) alkyl complexes through double silylation of iron(I) alkyl dinitrogen complexes to form an NNSi 2 group. Spectroscopically validated computations show that the disilylehydrazido(2−) ligand stabilizes the formal iron(IV) oxidation state through a strongly covalent Fe–N π-interaction, in which one π-bond fits an “inverted field” description. This means that the two bonding electrons are localized more on the metal than the ligand, and thus an iron(II) resonance structure is a significant contributor, similar to the previously-reported phenyl analogue. However, in contrast to the phenyl complex which has an S = 1 ground state, the ground state of the alkyl complex is S = 2, which places one electron in the π* orbital, leading to longer and weaker Fe–N bonds. The reactivity of these hydrazido(2−) complexes is dependent on the steric and electronic properties of the specific alkyl group. When the alkyl group is the bulky trimethylsilylmethyl, the formally iron(IV) species is stable at room temperature and no migration of the alkyl ligand is observed. However, the analogous complex with the smaller methyl ligand does indeed undergo migration of the carbon-based ligand to the NNSi 2 group to form a new N–C bond. This migration is followed by isomerization of the hydrazido ligand, and the product exists as two isomers that have distinct η 1 and η 2 binding of the hydrazido group. Lastly, when the alkyl group is benzyl, the Fe–C bond homolyzes to give a three-coordinate hydrazido(2−) complex which is likely due to the greater stability of a benzyl radical compared to that for methyl or trimethylsilylmethyl. These studies demonstrate the availability of a hydrocarbyl migration pathway at formally iron(IV) centers to form new N–C bonds directly to N 2 , though product selectivity is highly dependent on the identity of the migrating group.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA NTRS1982

Optogalvanic wavelength calibration for laser monitoring of reactive atmospheric species

Laser-based techniques have been successfully employed for monitoring atmospheric species of importance to stratospheric ozone chemistry or tropospheric air quality control. When spectroscopic methods using tunable lasers are used, a simultaneously recorded reference spectrum is required for wavelength calibration. For stable species this is readily achieved by incorporating into the sensing instrument a reference cell containing the species to be monitored. However, when the species of interest is short-lived, this approach is unsuitable. It is proposed that wavelength calibration for short-lived species may be achieved by generating the species of interest in an electrical or RF discharge and using optogalvanic detection as a simple, sensitive, and reliable means of recording calibration spectra. The wide applicability of this method is emphasized. Ultraviolet, visible, or infrared lasers, either CW or pulsed, may be used in aircraft, balloon, or shuttle experiments for sensing atoms, molecules, radicals, or ions.

Webster, C. R.↗

NASA NTRS1996

High Energy Density Matter for Rocket Propulsion

The objective of the High Energy Density Matter (HEDM) program is to identify, develop, and exploit high energy atomic and molecular systems as energetic sources for rocket propulsion applications. It is a high risk, high payoff program that incorporates both basic and applied research, experimental and theoretical efforts, and science and engineering efforts. The HEDM program is co-sponsored by the Air Force Office of Scientific Research (AFOSR) and the Phillips Laboratory (PURKS). It includes both in-house and contracted University/Industry efforts. Technology developed by the HEDM program offers the opportunity for significant breakthroughs in propulsion system capabilities over the current state-of-the-art. One area of great interest is the use of cryogenic solids to increase the density of the propellant and to act as a stable matrix for storage of energetic materials. No cryogenic solid propellant has ever been used in a rocket, and there remain engineering challenges to such a propellant. However, these solids would enable a wide class of highly energetic materials by providing an environment that is at very low temperatures and is a physical barrier to recombination or energy loss reactions. Previous to our experiments only hydrogen atoms had been isolated in solid hydrogen. To date we have succeeded in trapping B, Al, Li, N, and Mg atoms in solid H2. Small molecules, such as B2 and LiB, are also of interest. Current efforts involve the search for new energetic small molecules, increasing free radical concentrations up to 5 mole percent, and scale-up for propulsion testing.

Carrick, Patrick G.↗

DOE OSTI2023

Radical–Radical Reactions in Molecular Weight Growth: The Phenyl + Propargyl Reaction

The mechanism for hydrocarbon ring growth in sooting environments is still the subject of considerable debate. The reaction of phenyl radical (C 6 H 5 ) with propargyl radical (H 2 CCCH) provides an important prototype for radical–radical ring-growth pathways. We studied this reaction experimentally over the temperature range of 300–1000 K and pressure range of 4–10 Torr using time-resolved multiplexed photoionization mass spectrometry. We detect both the C 9 H 8 and C 9 H 7 + H product channels and report experimental isomer-resolved product branching fractions for the C 9 H 8 product. We compare these experiments to theoretical kinetics predictions from a recently published study augmented by new calculations. Here, these ab initio transition state theory-based master equation calculations employ high-quality potential energy surfaces, conventional transition state theory for the tight transition states, and direct CASPT2-based variable reaction coordinate transition state theory (VRC-TST) for the barrierless channels. At 300 K only the direct adducts from radical–radical addition are observed, with good agreement between experimental and theoretical branching fractions, supporting the VRC-TST calculations of the barrierless entrance channel. As the temperature is increased to 1000 K we observe two additional isomers, including indene, a two-ring polycyclic aromatic hydrocarbon, and a small amount of bimolecular products C 9 H 7 + H. Our calculated branching fractions for the phenyl + propargyl reaction predict significantly less indene than observed experimentally. We present further calculations and experimental evidence that the most likely cause of this discrepancy is the contribution of H atom reactions, both H + indenyl (C 9 H 7 ) recombination to indene and H-assisted isomerization that converts less stable C 9 H 8 isomers into indene. Especially at low pressures typical of laboratory investigations, H-atom-assisted isomerization needs to be considered. Regardless, the experimental observation of indene demonstrates that the title reaction leads, either directly or indirectly, to the formation of the second ring in polycyclic aromatic hydrocarbons.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2023

Beyond n-dopants for organic semiconductors: use of bibenzo[ d ]imidazoles in UV-promoted dehalogenation reactions of organic halides

2,2’-Bis(4-dimethylaminophenyl)- and 2,2'-dicyclohexyl-1,1',3,3'-tetramethyl-2,2',3,3'-tetrahydro-2,2'-bibenzo[ d ]imidazole ((N-DMBI) 2 and (Cyc-DMBI) 2 ) are quite strong reductants with effective potentials of ca. −2 V vs ferrocenium/ferrocene, yet are relatively stable to air due to the coupling of redox and bond-breaking processes. Here, we examine their use in accomplishing electron transfer-induced bond-cleavage reactions, specifically dehalogenations. The dimers reduce halides that have reduction potentials less cathodic than ca. −2 V vs ferrocenium/ferrocene, especially under UV photoexcitation (using a 365 nm LED). In the case of benzyl halides, the products are bibenzyl derivatives, whereas aryl halides are reduced to the corresponding arenes. The potentials of the halides that can be reduced in this way, quantum-chemical calculations, and steady-state and transient absorption spectroscopy suggest that UV irradiation accelerates the reactions via cleavage of the dimers to the corresponding radical monomers.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA NTRS1993

Design of a vehicle based system to prevent ozone loss

Reduced quantities of ozone in the atmosphere allow greater levels of ultraviolet light (UV) radiation to reach the earth's surface. This is known to cause skin cancer and mutations. Chlorine liberated from Chlorofluorocarbons (CFC's) and natural sources initiate the destruction of stratospheric ozone through a free radical chain reaction. The project goals are to understand the processes which contribute to stratospheric ozone loss, examine ways to prevent ozone loss, and design a vehicle-based system to carry out the prevention scheme. The 1992/1993 design objectives were to accomplish the first two goals and define the requirements for an implementation vehicle to be designed in detail starting next year. Many different ozone intervention schemes have been proposed though few have been researched and none have been tested. A scheme proposed by R.J. Cicerone, Scott Elliot and R.P.Turco late in 1991 was selected because of its research support and economic feasibility. This scheme uses hydrocarbon injected into the Antarctic ozone hole to form stable compounds with free chlorine, thus reducing ozone depletion. Because most polar ozone depletion takes place during a 3-4 week period each year, the hydrocarbon must be injected during this time window. A study of the hydrocarbon injection requirements determined that 100 aircraft traveling Mach 2.4 at a maximum altitude of 66,000 ft. would provide the most economic approach to preventing ozone loss. Each aircraft would require an 8,000 nm. range and be able to carry 35,000 lbs. of propane. The propane would be stored in a three-tank high pressure system. Missions would be based from airport regions located in South America and Australia. To best provide the requirements of mission analysis, an aircraft with L/D(sub cruise) = 10.5, SFC = 0.65 (the faculty advisor suggested that this number is too low) and a 250,000 lb TOGW was selected as a baseline. Modularity and multi-role functionality were selected to be key design features. Modularity provides ease of turnaround for the down-time critical mission. Multi-role functionality allows the aircraft to be used beyond its design mission, perhaps as an High Speed Civil Transport (HSCT) or for high altitude research.

Lynn, Sean R.↗

DOE OSTI2024

Flashback Measurements in Hydrogen Enriched Low Swirl Flames Using High Speed OH-PLIF

The fundamentals of stabilized flame dynamics and flashback events in a premixed low swirl burner (LSB) configuration are visualized experimentally using nanosecond (ns)-based high-speed hydroxyl radical planar laser-induced fluorescence (OH-PLIF). Swirlers with two different turning angles, 〖26〗^o and 〖33〗^o and three different center-body hole diameters, 1.08, 1.12 and 1.16 mm with measured swirl numbers varying from 0.43 to 0.49 are tested in this study at atmospheric temperature and pressure inlet conditions. An increase in flashback propensity is observed with increasing ϕ, X_(H_2 ) and decreasing V via detailed investigation of flame lift-off length (L) above the burner rim. Flashback ϕ (ϕ_FB) investigations show an expected linearly increasing trend with decreasing X_(H_2 ) and increasing V for each swirler studied and the results agree well with detailed L investigations in a stable flame configuration. ϕ_FB studies for different swirlers show an increase in flashback resistance with the increase in center-body hole diameter and swirl angle. Spatiotemporally resolved kHz-rate OH-PLIF is a promising technique to observe rapidly occurring flashback events and it can be applied for turbulence-chemistry interaction model validation.

Parajuli, Pradeep↗