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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 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Flame kinetics at scramjet-engine-relevant conditions: Role of prompt dissociation of weakly-bound radicals

Combustion in high-speed ram-based propulsion engines occurs under distinct thermodynamic conditions of high reactant temperatures (greater than 1000 K) and relatively low pressures (<5 atm). There is a lack of fundamental flame measurements at such conditions that result in adiabatic flame temperatures (T ad ) exceeding 2500 K. In this work, we have measured laminar flame speeds of oxygen-enriched CH 4 /oxidizer mixtures at sub-atmospheric conditions to probe kinetics at high T ad using the isobaric spherically expanding flame approach. Simulations with recent kinetic models revealed increasing differences between data and model predictions with increasing T ad , reaching up to 25 %. Kinetic analyses reveal that at the thermodynamic conditions in these O 2 -enriched flames, i.e., lower pressures and higher T ad , the effects of HCO prompt dissociation are accentuated. In addition to HCO, the prompt dissociations of CH 2 OH and C 2 H 5 are also considered. Here, the prompt dissociations of all three radicals were evaluated and their effects considered in flame speed simulations. Reaction path analysis for the present flames revealed that approximately half of the reaction flux for HCO formation undergoes prompt dissociation to H + CO. Furthermore, these analyses also revealed that the pathways and sensitive reactions are similar between oxygen-enriched fuel/oxidizer mixtures and preheated fuel/air mixtures, if both have similar T ad . Thus, flames of oxygen-enriched mixtures could be a surrogate to probe the flame chemistry of highly preheated mixtures at relatively low pressures that are often encountered in ram-based propulsion engine combustors.

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

Automated identification and calculation of prompt effects in kinetic mechanisms using statistical models

The kinetics of prompt dissociation involves rovibrationally excited species (generally formed by exothermic reactions) which may dissociate or isomerize prior to thermalization via collisions with the bath gas. Treating such rovibrationally excited species (so-called "hot" species) with standard kinetic phenomenology may result in incorrect macroscopic representation of their reactivity. Here this work presents the first fully automated methodology for the calculation of prompt effects of a chosen species in a kinetic mechanism, including (i) reaction selection; (ii) theoretical calculation of rate constants and prompt branching fractions; and (iii) final rate constant fitting. The energy partition between hot fragments is estimated using a variety of statistical models, including a new physically sound microcanonical statistical model based on the rovibrational density of states of the fragments. The methodology is validated against literature data for the prompt dissociations of HCO and C 3 H 7 radicals. The microcanonical statistical model is in better agreement with trajectory simulations for larger species and is thus applicable for practical systems that typically involve large molecules, for which direct dynamics calculations are impractical. The automated workflow is applied to the evaluation of the effects of prompt dissociation for two isomeric radicals C 4 H 7 1-3 (1-methylallyl) and C 4 H 7 1-4 (3-buten-1-yl). Twelve H-atom abstraction reactions are selected and the corresponding rate constants are computed with first principles theory. The microcanonical statistical model predicts that prompt dissociations of C 4 H 7 1-3 and C 4 H 7 1-4 are already significant at 1000K, resulting in differences of up to an order of magnitude at 2000K with respect to the phenomenological thermal rate constants. To illustrate the effects of prompt dissociation on simulations of experimental data, the calculated prompt rate constants are implemented in both CRECK and C3MechV3.3 kinetic mechanisms. Simulations of experimental flame data illustrate the noticeable impact of prompt dissociation kinetics on the high-temperature combustion reactivity of C 4 H 8 -1 and C 4 H 8 -2.

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

Dedication to James A. Miller

This special memorial issue pays tribute to James (Jim) A. Miller, a giant of combustion science who died in 2021, with a celebration of his enormous influence on the field. We were touched by the responses we received after we sent out the invitations for it. Jim inspired several generations of scientists, who viewed him as a mentor, a father figure, and a friend. Together with Nils Hansen and Peter Glarborg, we have written a detailed account on his life and work. Furthermore, it appeared in this journal shortly after his death; and so here we focus on the scientific areas he had interest in and influence on, and how they relate to the 34 papers in this issue. The topics of these papers span a variety of Jim's interests including nitrogen chemistry, polycyclic aromatic hydrocarbon (PAH) chemistry, oxidation chemistry, energy transfer, prompt dissociations, and codes to facilitate combustion chemistry simulations.

96 KNOWLEDGE MANAGEMENT AND PRESERVATION↗
DOE OSTI2025

Theoretically Informed Kinetics (ThInK): Establishing a modern C 0 -C 3 mechanism for combustion modeling

In contrast to the adage “Models are to be used, not believed”, combustion kinetics models have been intended to be predictive in nature. Theoretical chemical kinetics is now understood to provide a firm foundation for the reaction parameters, thereby facilitating predictive simulations of chemical reactivity, even in regimes that are poorly characterized by chemical kinetic and/or combustion experiments. In this study, we describe a theory-informed kinetics model (ThInK) for small molecule combustion chemistry (H 2 and C 1 – C 3 species) that is based on the prodigious use of theoretical predictions for reaction rate coefficients, thermochemistry, and transport parameters. The distinct features of this kinetics model, which was developed over the course of several decades, are illustrated through simulations of flame propagation and auto-ignition.

Energy transfer↗
DOE OSTI2024

Infrared signature of the hydroperoxyalkyl intermediate (·QOOH) in cyclohexane oxidation: An isomer-resolved spectroscopic study

Infrared (IR) action spectroscopy is utilized to characterize carbon-centered hydroperoxy-cyclohexyl radicals (·QOOH) transiently formed in cyclohexane oxidation. The oxidation pathway leads to three nearly degenerate ·QOOH isomers, β-, γ-, and δ-QOOH, which are generated in the laboratory by H-atom abstraction from the corresponding ring sites of the cyclohexyl hydroperoxide (CHHP) precursor. The IR spectral features of jet-cooled and stabilized ·QOOH radicals are observed from 3590 to 7010 cm −1 (∼10–20 kcal mol −1 ) at energies in the vicinity of the transition state (TS) barrier leading to OH radicals that are detected by ultraviolet laser-induced fluorescence. The experimental approach affords selective detection of β-QOOH, arising from its significantly lower TS barrier to OH products compared to γ and δ isomers, which results in rapid unimolecular decay and near unity branching to OH products. The observed IR spectrum of β-QOOH includes fundamental and overtone OH stretch transitions, overtone CH stretch transitions, and combination bands involving OH or CH stretch with lower frequency modes. The assignment of β-QOOH spectral features is guided by anharmonic frequencies and intensities computed using second-order vibrational perturbation theory. The overtone OH stretch (2ν OH ) of β-QOOH is shifted only a few wavenumbers from that observed for the CHHP precursor, yet they are readily distinguished by their prompt vs slow dissociation rates to OH products.

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

Strong field ionization and dissociation dynamics of vinyl bromide (C 2 H 3 Br) initiated by few-cycle pulses

Photoelectron-photoion (PEPICO) and photoion-photoion (PIPICO) coincidence measurements, coupled with a few-cycle intense laser field, were employed to investigate strong field ionization/dissociation dynamics of vinyl bromide (C₂H₃Br). The angular streaking technique was used to map the recoil-frame angle-dependent ionization rates to identify ionizing orbitals. Dissociative single ionization was mainly attributed to ionizing the lower lying molecular orbitals, suggesting that direct ionization dominates with few-cycle pulses. Three dissociative double ionization channels, both prompt and delayed fragmentation, were identified. Theoretical analysis using time-dependent configuration interaction with complex absorbing potential (TDCI-CAP) and high-level electronic structure methods was performed to elucidate the underlying ionization and dissociation mechanisms.

Olowolafe, Temitayo A. [Wayne State University, De↗
NASA NTRS1992

g-factors of the SH (0-0) band and SH upper limit in Comet P/Brorsen-Metcalf (1989o)

A search for SH, the prime dissociative product of H2S, has been prompted by the microwave-band detection of H2S in Comets Austin and Levy. Attention is accordingly given here to g-factors for the A-X (0-0) band of SH as a function of heliocentric velocity at a heliocentric distance of 1 AU. An upper-limit production rate for SH relative to water of 0.017 is derived for the case of Comet P/Brorsen-Metcalf. A dissociative lifetime of 105 sec, at 1 AU heliocentric distance, and a heliocentric velocity of -28.5 km/sec, are also obtained.

Kim, Sang J.↗
NASA NTRS1996

Fullerene Propellant Research for Electric Propulsion

The large mass, low first ionization potential and large electron impact ionization cross-section make Buckminsterfullerene (carbon 60) potentially attractive as an ion engine propellant. It has the potential for significant increases in engine efficiency over that obtained with xenon at specific impulses less than 3 000 s. One problem encountered in fullerene ion engines has been dissociation of the propellant. Previously this was attributed to thermal decomposition due to operation of the ion engine at temperatures greater than 1073 K. However, during tests conducted at temperatures lower than 1073 K fullerene fragmentation was still observed. This prompted an investigation to determine if the dissociation was still due to thermal effects or if it was due to collisional processes in the discharge chamber.

fullerenes↗
DOE OSTI2024

Prompt and non-prompt J/$ψ$ production at midrapidity in Pb–Pb collisions at $\sqrt{s_{\textrm{NN}}}$ = 5.02 TeV

The transverse momentum (p T ) and centrality dependence of the nuclear modif cation factor R AA of prompt and non-prompt J/ψ, the latter originating from the weak decays of beauty hadrons, have been measured by the ALICE collaboration in Pb–Pb collisions at $\sqrt{s_{\textrm{NN}}}$ = 5.02 TeV. The measurements are carried out through the e + e - decay channel at midrapidity (|y| < 0.9) in the transverse momentum region 1.5 < p T < 10 GeV/c. Both prompt and non-prompt J/ψ measurements indicate a significant suppression for p T > 5 GeV/c, which becomes stronger with increasing collision centrality. The results are consistent with similar LHC measurements in the overlapping p T intervals, and cover the kinematic region down to p T = 1.5 GeV/c at midrapidity, not accessible by other LHC experiments. The suppression of prompt J/ψ in central and semicentral collisions exhibits a decreasing trend towards lower transverse momentum, described within uncertainties by models implementing J/ψ production from recombination of $c$ and $\overline{c}$ quarks produced independently in different partonic scatterings. At high transverse momentum, transport models including quarkonium dissociation are able to describe the suppression for prompt J/ψ. For non-prompt J/ψ, the suppression predicted by models including both collisional and radiative processes for the computation of the beauty-quark energy loss inside the quark-gluon plasma is consistent with measurements within uncertainties.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2024

Fraction of χ c Decays in Prompt J / ψ Production Measured in p Pb Collisions at s NN = 8.16 TeV

The fraction of χ c 1 and χ c 2 decays in the prompt J / ψ yield, F χ c → J / ψ = σ χ c → J / ψ / σ J / ψ , is measured by the LHCb detector in p Pb collisions at s NN = 8.16 TeV . The study covers the forward ( 1.5 < y * < 4.0 ) and backward ( − 5.0 < y * < − 2.5 ) rapidity regions, where y * is the J / ψ rapidity in the nucleon-nucleon center-of-mass system. Forward and backward rapidity samples correspond to integrated luminosities of 13.6 ± 0.3 and 20.8 ± 0.5 nb − 1 , respectively. The result is presented as a function of the J / ψ transverse momentum p T , J / ψ in the range 1 < p T , J / ψ < 20 GeV / c . The F χ c → J / ψ fraction at forward rapidity is compatible with the LHCb measurement performed in p p collisions at s = 7 TeV , whereas the result at backward rapidity is 2.4 σ larger than in the forward region for 1 < p T , J / ψ < 3 GeV / c . The increase of F χ c → J / ψ at low p T , J / ψ at backward rapidity is compatible with the suppression of the ψ ( 2 S ) contribution to the prompt J / ψ yield. The lack of in-medium dissociation of χ c states observed in this study sets an upper limit of 180 MeV on the free energy available in these p Pb collisions to dissociate or inhibit charmonium state formation. © 2024 CERN, for the LHCb Collaboration 2024 CERN

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
NASA NTRS1995

Characterization of the Minimum Energy Path for the Reaction of Singlet Methylene with N2: The Role of Singlet Methylene in Prompt NO

We report calculations of the minimum energy pathways connecting CH2 + N2 to diazomethane and diazirine, for the rearrangement of diazirine to diazomethane, for the dissociation of diazirine to HCN2+H, and of diazomethane to CH2N+N. The calculations use Complete Active Space Self-Consistent Field (CASSCF) derivative methods to characterize the stationary points and Internally Contracted Configuration Interaction (ICCI) to determine the energetics. The calculations suggest a potential new source of prompt NO from the reaction CH2 with N2 to give diazirine, and subsequent reaction of diazirine with hydrogen abstracters to form doublet HCN2, which leads to HCN+N(S-4) on the previously studied CH+N2 surface. The calculations also predict accurate 0 K heats of formation of 77.7 kcal/mol and 68.0 kcal/mol for diazirine and diazomethane, respectively.

Walch, Stephen P.↗
NASA NTRS1995

Characterization of the Minimum Energy Path for the Reaction of Singlet Methylene with N2: The Role of Singlet Methylene in Prompt NO

We report calculations of the minimum energy pathways connecting (1)CH2+N2 to diazomethane and diazirine, for the rearrangement of diazirine to diazomethane, for the dissociation of diazirine to HCN2+H, and of diazomethane to CH2N+N. The calculations use complete active space self-consistent field (CASSCF) derivative methods to characterize the stationary points and internally contracted configuration interaction (ICCI) to determine the energetics. The calculations suggest a potential new source of prompt NO from the reaction of (1)CH2 with N2 to give diazirine, and subsequent reaction of diazirine with hydrogen abstracters to form doublet HCN2, which leads to HCN+N(S-4) on the previously studied CH+N2 Surface. The calculations also predict accurate 0 K heats of formation of 77.7 kcal/mol and 68.0 kcal/mol for diazirine and diazomethane, respectively.

Walch, Stephen P.↗
DOE OSTI2026

Resolving Competing Ultraviolet Photoinduced Ring-Opening and Dissociation Pathways in Iodothiophenes by Ultrafast Electron Diffraction

The ultraviolet photochemistry of halothiophenes is thought to proceed via competing pathways, prompt C–X (X = halogen) bond fission, and parent ring opening followed by fragmentation, yet direct structural evidence distinguishing these mechanisms is limited. Here, time-resolved gas-phase ultrafast electron diffraction (UED) has been used to directly follow the structural dynamics of 2- and 3-iodothiophene following photoexcitation at 247 nm. For both isomers, the time-resolved pair distribution functions reveal the appearance of new interatomic distances that cannot be explained by simple C–I bond cleavage and formation of C 4 SH 3 radical cofragments. The signatures, particularly those for 2-iodothiophene, are consistent with a rival ring-opening channel of the intact parent, which evolve on time scales distinct from those associated with the direct C–I bond cleavage. In addition, the extracted kinetics indicate that the ring-opening channel occurs faster in 2-iodothiophene than in the 3-isomer at this excitation wavelength. Furthermore, these measurements provide direct geometric evidence for competing pathways leading to different structures following photodissociation in a model heteroaromatic and further establish UED as a sensitive probe of complex excited-state chemistry.

Bond cleavage↗
NASA NTRS1985

Products and yields from O3 photodissociation at 1576 A

An analysis has been made of the primary atomic and molecular products arising from O3 photodissociation at 1576 A. The yield of oxygen atoms is 1.90 + or - 0.30, of which 71 percent are O(3P) and 29 percent are O(1D). Since a primary yield greater than unity can only be a consequence of three-fragment dissociation, these results suggest that fragmentation into three O(3P) atoms, and production of O(1D) plus a singlet oxygen molecule, have comparable yields. Observation of prompt emission in the 7300-8100 A spectral region indicates that the singlet O2 is O2(b 1Sigma + g). Vibrational levels in the range v = 0-6 have been detected, the distribution corresponding to a vibrational temperature of 1000 K.

Taherian, M. R.↗
DOE OSTI2026

Mechanism, Thermochemistry, and Kinetics for the CH + N 2 Reaction Leading to Prompt NO Formation in Combustion

Here, the reaction of CH + N 2 forming H + NCN is a remarkable example of activation of the nitrogen triple bond and is an important source of prompt NO in combustion. The reaction pathway is complex and proceeds through two competing mechanisms: a cyclic addition channel initiated by c-HC(NN) and a chain-addition channel initiated by HCNN, both of which eventually form HNCN prior to dissociation to H + NCN. This work reinvestigates this reaction with composite coupled cluster protocols, including a novel spin-flip equation of motion coupled cluster scheme, combined with pragmatic two-dimensional master equation simulations of the resulting rate coefficients. These improved calculations predict the CH + N 2 rate coefficient between the two more recent previous theoretical results and reduce the uncertainties of the best theoretical models of this reaction to less than a factor of 1.3. Additionally, we provide a closer theoretical investigation of the simultaneous dependence of the CH + N 2 rate coefficient on pressure and temperature, and affirm that collisionally stabilized HNCN, another potential source of prompt NO, emerges as an appreciable product of this reaction under conditions relevant to automotive internal combustion engines and aircraft gas turbine engines.

Nguyen, Thanh Lam [Univ. of Florida, Gainesville, ↗
NASA NTRS1987

The effect of neutrino transport on the collapse of iron stellar cores

A multigroup flux-limited diffusion approximation to neutrino transport, correct to first order in material velocities, is described. The role of neutrino-electron scattering in determining core deleptonization is studied using a modified Fokker-Planck approximation in which adjacent neutrino energy groups are coupled. The moderate deleptonizaton obtained during infall restricts homologous core masses to less than 0.8 solar mass. With 0.6-0.8 solar mass of outer core to traverse, nuclear dissociation alone stalls the shock waves produced at core bounce. In addition, neutrino energy losses remove at least another 4 x 10 to the 51st ergs. In no case is matter ejected promptly as a direct result of the initial shock wave.

Myra, E. S.↗
NASA NTRS1994

Detection of CO Cameron band emission in comet P/Hartley 2 (1991 XV) with the Hubble Space Telescope

Ultraviolet (UV) spectra of comet P/Hartley 2 (1991 XV) taken with the Faint Object Spectrograph (FOS) on the Hubble Space Telescope (HST) in 1991 September reveal several bands of the Cameron system of CO (a 3 Pi-X 1 Sigma). These band are most likely due to 'prompt' emission from CO2 and, thus, provide a direct tracer of the CO2 abundance in the nucleus. Photodissociative excitation of CO2 is probably the largest contributor to the Cameron band emission, but significant contributions from electron impact excitation of CO, electron impact dissociation of CO2, and dissociative recombination of CO2(+), are also possible. Using our estimate that photodissociative excitation is responsible for approximately 60% of the total excitation of the Cameron system, we derive Q(sub CO2) approximately 2.6 x 10(exp 27) molecules/s, which implies CO2/H20 approximately 4%. If all of the Cameron band emission is due to photodissociative excitation, then CO2/H2O = 7 +/- 2%. For the largest possible contributions from the other excitation mechanisms considered, the CO2 abundance could be as a small as aproximately 2-3%. We did not detect CO Fourth Positive Group emission in our data and derive an upper limit of CO/H2O less than or equal to 1% (3 sigma) for CO coming directly from the nucleus. Comparison of the relative CO2 and CO abundances in P/Hartley 2 to those in P/Halley (CO2/H2O approximately 3%-4%, CO/H20 approximately 4% for the nucleus source) indicates that selective devolatilization of the nucleus may have occurred for P/Hartley 2. A relatively large CO2/CO ratio (i.e., approximately greater than 1) seems to be a common property of cometary nuclei. Since gas phase chemistry, in either the solar nebula or the interstellar medium (ISM), appears incapable of producing large relative CO2 abundances, the CO2 in cometary nuclei is probably produced either by UV and/or cosmic ray irradiation of ISM grains prior to the formation of the Solar System, or by condensation fractionation in the solar nebula.

Weaver, H. A.↗
DOE OSTI2024

Resolving Discrepancies Between Theory and Experiment for the NCN + H Reaction

Flame modeling studies have highlighted the role of branching in the kinetics for the prompt NO switch reaction, NCN + H. In this reaction, there is strong competition between the CH + N2 (R1) and HCN + N (R2) product channels. Increased branching towards reaction R2 promotes the subsequent formation of Fenimore or Prompt NO. Recent direct shock tube studies on this complex reaction conclude that branching to reaction R2 is much more favorable than the predicted branching from theoretical studies. The experimentally predicted prompt NO switch temperature (TS), i.e., the temperature at which k2/(k1+k2) = 0.5, is at 1670 K, in contrast to theory that predicts Ts > 3200 K. The present theory/modeling work was initiated to highlight potential causes for this significant discrepancy between experiment and theory. Our analysis of the simulations reported in the experimental studies indicate that including a fall-off representation for C2H5 radical dissociation (with C2H5 produced from C2H5I dissociation and acting as an H-atom source) has a noticeable influence on the simulations for NCN decay and HCN formation in the shock tube studies. With the inclusion of a theory-based pressure fall-off representation for C2H5 dissociation, we show that this radical persists for much longer timescales even at the high-temperatures in the shock tube studies. This persistence then facilitates the rapid conversion of reactive H-atoms to CH3 radicals at the shock tube conditions via the H + C2H5 → CH3 + CH3 reaction. An updated theoretical analysis for this classic addition-elimination reaction is also provided in this work. The rapid formation of CH3 radicals necessitates the inclusion of additional reactions to adequately simulate the NCN and HCN data. Our simulations conclude that, with the inclusion of these additional reactions, the NCN and HCN profiles can be reasonably well simulated by the most recent theoretical predictions.

Ethyl Radicals↗