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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 37 records · Page 2
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

The role of energy transfer and competing bimolecular reactions in characterizing the unimolecular dissociations of allylic radicals

Resonantly stabilized radicals (RSR's) such as allylic radicals typically have bond energies exceeding 45 kcal/mol and are therefore reasonably long-lived up to quite high temperatures. Consequently, kinetics of the unimolecular dissociations and bimolecular reactions of these long-lived RSR's assume significance in high temperature chemically reacting systems such as in flames. Our recent analyses (J. Cho et al., Proc. Comb. Inst., 2022) of the uncertainty propagated by the energy transfer parameters for 1-methylallyl (1MA) dissociation to the laminar flame speed, indicates an intricate coupling between the kinetics of 1MA dissociation (chain propagation) and its reaction with H-atoms (chain-termination). Here, this work extends such analyses to other C 3 – C 5 allylic radicals: allyl, 2-methylallyl, 1,1-dimethylallyl, 1,2-dimethylallyl, and 1,3-dimethylallyl. Theoretical kinetics for the C 3 – C 4 allylic radicals were taken from prior literature studies (J.A. Miller et al., J. Phys. Chem., 2008; J. Cho et al., Proc. Comb. Inst., 2022; R.S. Tranter et al., Proc. Comb. Inst., 2017). Potential energy surfaces were newly computed for the dissociations of the larger C5 allylic radicals and the reactions of these radicals with H-atoms. These PES's were then used to calculate rate constants for the relevant unimolecular and bimolecular reactions. Energy transfer has a crucial role to play in these pressure-dependent reactions and therefore the present kinetics calculations relied on a-priori predictions of collisional energy transfer parameters to best characterize the branching between chain propagating unimolecular dissociations of these allylic radicals and chain terminating bimolecular reactions of these RSR's with H-atoms. Prompt dissociations are now established to be a universal feature of free radical dissociations. Here we have also characterized the propensity for prompt dissociations in these more-stable allylic RSR's and their role in combustion simulations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
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

OH Roaming and Beyond in the Unimolecular Decay of the Methyl-Ethyl-Substituted Criegee Intermediate: Observations and Predictions

Alkene ozonolysis generates short-lived Criegee intermediates that are a significant source of hydroxyl (OH) radicals. Here this study demonstrates that roaming of the separating OH radicals can yield alternate hydroxycarbonyl products, thereby reducing the OH yield. Specifically, hydroxybutanone has been detected as a stable product arising from roaming in the unimolecular decay of the methyl-ethyl-substituted Criegee intermediate (MECI) under thermal flow cell conditions. The dynamical features of this novel multistage dissociation plus a roaming unimolecular decay process have also been examined with ab initio kinetics calculations. Experimentally, hydroxybutanone isomers are distinguished from the isomeric MECI by their higher ionization threshold and distinctive photoionization spectra. Moreover, the exponential rise of the hydroxybutanone kinetic time profile matches that for the unimolecular decay of MECI. A weaker methyl vinyl ketone (MVK) photoionization signal is also attributed to OH roaming. Complementary multireference electronic structure calculations have been utilized to map the unimolecular decay pathways for MECI, starting with 1,4 H atom transfer from a methyl or methylene group to the terminal oxygen, followed by roaming of the separating OH and butanonyl radicals in the long-range region of the potential. Roaming via reorientation and the addition of OH to the vinyl group of butanonyl is shown to yield hydroxybutanone, and subsequent C–O elongation and H-transfer can lead to MVK. A comprehensive theoretical kinetic analysis has been conducted to evaluate rate constants and branching yields (ca. 10–11%) for thermal unimolecular decay of MECI to conventional and roaming products under laboratory and atmospheric conditions, consistent with the estimated experimental yield (ca. 7%).

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

Carbon‐13 Hyperpolarization of α‐Ketocarboxylates with Parahydrogen in Reversible Exchange

Abstract Signal Amplification by Reversible Exchange (SABRE) is a relatively simple and fast hyperpolarization technique that has been used to hyperpolarize the α‐ketocarboxylate pyruvate, a central metabolite and the leading hyperpolarized MRI contrast agent. In this work, we show that SABRE can readily be extended to hyperpolarize 13 C nuclei at natural abundance on many other α‐ketocarboxylates. Hyperpolarization is observed and optimized on pyruvate (P 13C =17 %) and 2‐oxobutyrate (P 13C =25 %) with alkyl chains in the R‐group, oxaloacetate (P 13C =11 %) and alpha‐ketoglutarate (P 13C =13 %) with carboxylate moieties in the R group, and phenylpyruvate (P 13C =2 %) and phenylglyoxylate (P 13C =2 %) with phenyl rings in the R‐group. New catalytically active SABRE binding motifs of the substrates to the hyperpolarization transfer catalyst – particularly for oxaloacetate – are observed. We experimentally explore the connection between temperature and exchange rates for all of these SABRE systems and develop a theoretical kinetic model, which is used to fit the hyperpolarization build‐up and decay during SABRE activity.

McBride, Stephen J. [Department of Chemistry North↗
DOE OSTI2023

Electrostatic upper-hybrid mode instability driven by a ring electron distribution

Quasi electrostatic fluctuations in the upper-hybrid frequency range are commonly detected in the planetary magnetospheric environment. The origin of such phenomena may relate to the instability driven by a loss-cone feature associated with the electrons populating the dipole-like magnetic field. The present paper carries out a one-dimensional electrostatic particle-in-cell simulation accompanied by a reduced quasilinear kinetic theoretical analysis to investigate the dynamics of the upper-hybrid mode instability driven by an initial ring electron distribution function, which is a form of loss-cone distribution. A favorable comparison is found between the two approaches, which shows that the reduced quasilinear theory, which is grounded in the concept of a model of the particle distribution function that is assumed to maintain a fixed mathematical form except that the macroscopic parameters that define the distribution are allowed to evolve in time, can be an effective tool in the study of plasma instabilities, especially if it is guided by and validated against the more rigorous simulation result.

Physics↗
DOE OSTI2022

Graph-theoretical KMC Framework for Calculating Effective Diffusivity in TPBAR Components: Effective Diffusivity of Tritium in α-Zr Grain Boundaries

We report the development of a computer simulation tool based on the Graph-theoretical kinetic Monte Carlo (GT-KMC) approach that can be used to simulate diffusion and derive effective diffusivity of species in complex structures of TPBAR components. The GT-KMC framework was implemented in AKSOME, an on-lattice self-learning kinetic Monte Carlo tool developed at PNNL and was previously used to study solute diffusion in metal alloys. This newly developed tool will be helpful in simulating atom diffusion and extracting their effective diffusivities in grain boundaries and interfaces in various TPBAR components. Once benchmarked, the tool will be used to simulate the diffusion of tritium (hydrogen) along grain boundaries in α-Zr using the activation energy barrier data previously obtained from Density Functional Theory calculations.

36 MATERIALS SCIENCE↗
NASA NTRS1973

Turbojet emissions, hydrogen versus JP

Preliminary data from an experimental combustor show that the NOx emission index, g(NO2)/Kg fuel, is about three times greater for hydrogen than for JP at simulated cruise conditions. However, if these results are applied to aircraft designed for a given mission, hydrogen's higher heating value enables the aircraft to have a lower gross weight and a lower fuel flow rate so that the NOx emission rate, Kg (NO2)/hr may be reduced about 30 percent compared to JP. Theoretical kinetics calculations indicate that combustors may be designed for hydrogen that could further decrease NOx emissions by taking advantage of hydrogen's wide flammable limits and high burning velocity.

Grobman, J.↗
NASA NTRS1973

Turbojet emissions - Hydrogen versus JP.

Preliminary data from an experimental combustor show that the NO sub x emission index, g (NO2)/kg fuel, is about three times greater for hydrogen than for JP at simulated cruise conditions. However, if these results are applied to aircraft designed for a given mission, hydrogen's higher heating value enables the aircraft to have a lower gross weight and a lower fuel flow rate so that the NO sub x emission rate, kg(NO2)/hr may be reduced about 30% compared to JP. Theoretical kinetics calculations indicate that combustors may be designed for hydrogen that could further decrease NO sub x emissions by taking advantage of hydrogen's wide flammable limits and high burning velocity.

Grobman, J.↗
NASA NTRS1976

Electrochemical performance investigations on the hydrogen depolarized CO2 concentrator

An extensive investigation of anode and cathode polarization in complete cells and half cells was conducted to determine the factors affecting HDC electrode polarization and the nature of this polarization. Matrix-electrolyte-electrode interactions and cell electrolyte composition were also investigated. The electrodes were found to have normal performance capabilities. The HDC anode polarization characteristics were correlated with a theoretical kinetic analysis; and, except for some quantitative details, a rather complete understanding of the causes for HDC electrode polarization was formulated. One of the important finding resulting from the kinetic analysis was that platinum appears to catalyze the decomposition of carbonic acid to carbon dioxide and water. It was concluded that the abnormal voltage performance of the One Man ARS HDC cells was caused by insufficient cell electrolyte volume under normal operating conditions due to deficiencies in the reservoir to cell interfacing.

Aylward, J. R.↗
NASA NTRS2004

Computational studies of Ras and PI3K

Until recently, experimental techniques in molecular cell biology have been the primary means to investigate biological risk upon space radiation. However, computational modeling provides an alternative theoretical approach, which utilizes various computational tools to simulate proteins, nucleotides, and their interactions. In this study, we are focused on using molecular mechanics (MM) and molecular dynamics (MD) to study the mechanism of protein-protein binding and to estimate the binding free energy between proteins. Ras is a key element in a variety of cell processes, and its activation of phosphoinositide 3-kinase (PI3K) is important for survival of transformed cells. Different computational approaches for this particular study are presented to calculate the solvation energies and binding free energies of H-Ras and PI3K. The goal of this study is to establish computational methods to investigate the roles of different proteins played in the cellular responses to space radiation, including modification of protein function through gene mutation, and to support the studies in molecular cell biology and theoretical kinetics models for our risk assessment project.

Ren, Lei↗
DOE OSTI2020

Direct kinetic measurements and theoretical predictions of an isoprene-derived Criegee intermediate

Isoprene has the highest emission into Earth’s atmosphere of any nonmethane hydrocarbon. Atmospheric processing of alkenes, including isoprene, via ozonolysis leads to the formation of zwitterionic reactive intermediates, known as Criegee intermediates (CIs). Direct studies have revealed that reactions involving simple CIs can significantly impact the tropospheric oxidizing capacity, enhance particulate formation, and degrade local air quality. Methyl vinyl ketone oxide (MVK-oxide) is a four-carbon, asymmetric, resonance-stabilized CI, produced with 21 to 23% yield from isoprene ozonolysis, yet its reactivity has not been directly studied. We present direct kinetic measurements of MVK-oxide reactions with key atmospheric species using absorption spectroscopy. Direct UV-Vis absorption spectra from two independent flow cell experiments overlap with the molecular beam UV-Vis-depletion spectra reported recently [M. F. Vansco, B. Marchetti, M. I. Lester, J. Chem. Phys. 149, 44309 (2018)] but suggest different conformer distributions under jet-cooled and thermal conditions. Comparison of the experimental lifetime herein with theory indicates only the syn -conformers are observed; anti -conformers are calculated to be removed much more rapidly via unimolecular decay. We observe experimentally and predict theoretically fast reaction of syn -MVK-oxide with SO 2 and formic acid, similar to smaller alkyl-substituted CIs, and by contrast, slow removal in the presence of water. We determine products through complementary multiplexed photoionization mass spectrometry, observing SO 3 and identifying organic hydroperoxide formation from reaction with SO 2 and formic acid, respectively. The tropospheric implications of these reactions are evaluated using a global chemistry and transport model.

09 BIOMASS FUELS↗
DOE OSTI2022

Non-Idealities in Lab-Scale Kinetic Testing: A Theoretical Study of a Modular Temkin Reactor

The Temkin reactor can be applied for industrial relevant catalyst testing with unmodified catalyst particles. It was assumed in the literature that this reactor behaves as a cascade of continuously stirred tank reactors (CSTR). However, this assumption was based only on outlet gas composition or inert residence time distribution measurements. The present work theoretically investigates the catalytic CO2 methanation as a test case on different catalyst geometries, a sphere, and a ring, inside a single Temkin reaction chamber under isothermal conditions. Axial gas-phase species profiles from detailed computational fluid dynamics (CFD) are compared with a CSTR and 1D plug-flow reactor (PFR) model using a sophisticated microkinetic model. In addition, a 1D chemical reactor network (CRN) model was developed, and model parameters were adjusted based on the CFD simulations. Whereas the ideal reactor models overpredict the axial product concentrations, the CRN model results agree well with the CFD simulations, especially under low to medium flow rates. This study shows that complex flow patterns greatly influence species fields inside the Temkin reactor. Although residence time measurements suggest CSTR-like behavior, the reactive flow cannot be described by either a CSTR or PFR model but with the developed CRN model.

Wehinger, Gregor D. (ORCID:0000000217743391)↗
DOE OSTI2021

Combustion chemistry in the twenty-first century: Developing theory-informed chemical kinetics models

Over the past 20 to 25 years theoretical chemistry (particularly theoretical chemical kinetics) has played an increasingly important role in developing chemical kinetics models for combustion. Theoretical methods of obtaining rate parameters are now competitive in accuracy with experiment, particularly for small molecules. Moreover, theoretical methods can deal with conditions that experiments frequently cannot. In addition to increased accuracy, theory has rejuvenated methods and discovered phenomena that were completely unappreciated, or at least underappreciated, in the 20th century. Our primary interest here is in molecular-level issues, i.e. in calculating rate and transport parameters. However, dealing with kinetics models that involve thousands of reactions and hundreds of species is important for practical applications and is relatively new to the 21st century. Theory, in a general sense, and theoretical methods development have a role to play here too. We discuss in this review all these topics in some detail with an emphasis on issues and methods that have emerged in the last 20 years or so. Even so, our review is selective, rather than comprehensive, out of necessity.

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

Approaching PetaVolts per Meter Plasmonics Using Structured Semiconductors

A newly uncovered class of plasmons in the strongly excited limit opens access to unprecedented Petavolts per meter electromagnetic fields with wide-ranging, transformative impact. Unlike conventional plasmons, such plasmons are constituted by non-perturbative, large-amplitude oscillations of the ultradense, delocalized free electron Fermi gas inherent in conductive media. Here structured semiconductors doped to have an appropriate conduction electron density are introduced to tune the properties of the Fermi gas for matched excitation of large-amplitude plasmons using readily available electron beams which enables immediate experimental validation. Specifically, an electrostatic, surface “crunch-in” plasmon is collisionlessly excited by the beam launched inside a tube. Strong excitation due to matching results in relativistic oscillations of the electron gas and unravels unique phenomena. Relativistically induced ballistic electron transport comes about due to relativistic multifold increase in the mean free path and also leads to unconventional heat deposition beyond Ohm’s law. This explains the absence of observed damage or solid-plasma formation in past experiments on conductive samples interacting with electron bunches shorter than 10-13 seconds. Furthermore, relativistic momentum leads to copious tunneling of electron gas across the surface, which then crunches inside the tube. Relativistic effects along with large, localized electron density variations underlying these modes necessitate kinetic approach to theoretical and computational modeling. Kinetic model presented here demonstrates experimental viability of observing tens of gigavolts per meter plasmonic fields excited by matching readily available electron beams to plasmons in semiconductors with 1018cm-3 free electron density, and paves the way for Petavolts per meter plasmonics.

42 ENGINEERING↗