REACTION ZONE AND STABILITY OF GASEOUS DETONATIONS
Reaction zone and stability of gaseous detonations - gas dyamics
GAS DYNAMICS↗
SEARCH · Engineering Papers
Results for “Chemical reaction dynamics”
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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Enabling accurate chemical modeling of shocked energetic materials using a machine learning interatomic potential
Understanding the complex chemistry of organic materials under dynamic compression is important for many applications, but it is challenging due to the large number of reactions occurring at various time scales. Here, in this study, we develop a machine learning potential based on Chebyshev polynomials to study the insensitive energetic material 1,3,5-triamino-2,4,6-trinitrobenzene (TATB) under detonation. We discuss a strategy for constructing diverse training data needed to capture the complex chemistry of TATB. Our potential demonstrates strong transferability across a wide range of thermodynamic conditions and other explosives, enabling accurate and reliable chemical modeling of organic materials under extreme conditions. The efficiency of our approach allows for simulations over several nanoseconds and for large system sizes, providing detailed insights into the chemistry of shocked TATB. The model accurately reproduces experimental Hugoniot equation of state data, and our simulations reveal the rapid formation of nitrogen-rich carbon clusters following shock. The methods and datasets developed here offer a robust framework for accurate chemical modeling of other shocked organic energetic materials.
Chemistry↗
Three-Dimensional CFD Investigation of Pre-Spark Heat Release in a Boosted SI Engine
Low-temperature heat release (LTHR) in spark-ignited internal combustion engines is a critical step toward the occurrence of auto-ignition, which can lead to an undesirable phenomenon known as engine knock. As such, correct predictions of LTHR are of utmost importance to improve the understanding of knock and enable techniques aimed at controlling it. While LTHR is typically obscured by the deflagration following the spark ignition, extremely late ignition timings can lead to LTHR occurrence prior to the spark, i.e., pre-spark heat release (PSHR). In this research, PSHR in a boosted direct-injection SI engine was numerically investigated using three-dimensional computational fluid dynamics (CFD). A hybrid approach was used, based on the G-equation model for representing the turbulent flame front and the multi-zone well-stirred reactor model for tracking the chemical reactions within the unburnt region. A recently developed best practice was also employed which keeps the well-stirred reactor model active throughout the entire simulation. This allowed for correct predictions of the previous cycle trapped residuals which have a considerable effect on the onset of LTHR. Multi-cycle simulations were conducted using Co-Optima alkylate and E30 fuels. The predicted in-cylinder pressure and heat release rate agreed well with the experimental data and served as validation for the CFD model. Following the initial validation, the dynamics of PSHR was discussed and a series of parameters of interest were assessed. First, the effect of exhaust valve temperature was investigated, qualitatively highlighting the importance of boundary conditions uncertainty. Further analyses were carried out on the effects of fuel properties, including laminar flame speed (LFS) and heat of vaporization (HOV). The results indicate that PSHR phasing is slightly advanced with lower LFS as more trapped unburnt fuel is made available for the next cycle. A similar trend was observed with lower HOV as less intense spray cooling led to higher mixture temperatures, i.e., higher mixture reactivity. Finally, a comparison of Co-Optima alkylate and E30 fuels was made using the pressure-temperature trajectory framework. It was shown that the differences between Co-Optima alkylate and E30 in PSHR tendency are correlated with both HOV and chemical effects.
33 ADVANCED PROPULSION SYSTEMS↗
Exploration of Electrochemical Reactions at Organic–Inorganic Halide Perovskite Interfaces via Machine Learning in In Situ Time-of-Flight Secondary Ion Mass Spectrometry
The instability of hybrid organic–inorganic perovskite (HOIP) devices is one of the significant challenges preventing commercialization. Exploring these phenomena is severely limited by the complexity of the intrinsic electrochemistry of HOIPs, the presence of multiple volatile and mobile ionic species, and the possible role of environmentally induced reactions at surfaces and triple-phase junctions. Here, in situ studies of the electrochemistry of methylammonium lead bromide perovskite with the Au electrode interface are reported via light- and voltage-dependent time-of-flight secondary ion mass spectrometry (ToF-SIMS) imaging of lateral perovskite heterostructures. While ToF-SIMS allows for the visualization of the chemical composition along the surface and its evolution with light and electrical bias, the interpretation of the multidimensional data obtained is often limited due to strong correlations between chemical signatures and the need to track multiple peaks at once. Here, a machine learning workflow combining the Hough transform and non-negative matrix factorization and no-negative tensor decomposition is developed to avoid this limitation and extract salient features of associated chemical changes and to separate the light- and voltage-dependent dynamics. Finally, combining these in situ characterizations and the machine learning workflow provides comprehensive information on the chemical nature of moving species, ion accumulation, and interfacial electrochemical reactions in HOIP devices.
36 MATERIALS SCIENCE↗
Development and Evaluation of Chemistry‐Aerosol‐Climate Model CAM5‐Chem‐MAM7‐MOSAIC: Global Atmospheric Distribution and Radiative Effects of Nitrate Aerosol
Abstract An advanced aerosol treatment, with a focus on semivolatile nitrate formation, is introduced into the Community Atmosphere Model version 5 with interactive chemistry (CAM5‐chem) by coupling the Model for Simulating Aerosol Interactions and Chemistry (MOSAIC) with the 7‐mode Modal Aerosol Module (MAM7). An important feature of MOSAIC is dynamic partitioning of all condensable gases to the different fine and coarse mode aerosols, as governed by mode‐resolved thermodynamics and heterogeneous chemical reactions. Applied in the free‐running mode from 1995 to 2005 with prescribed historical climatological conditions, the model simulates global distributions of sulfate, nitrate, and ammonium in good agreement with observations and previous studies. Inclusion of nitrate resulted in ∼10% higher global average accumulation mode number concentrations, indicating enhanced growth of Aitken mode aerosols from nitrate formation. While the simulated accumulation mode nitrate burdens are high over the anthropogenic source regions, the sea‐salt and dust modes respectively constitute about 74% and 17% of the annual global average nitrate burden. Regional clear‐sky shortwave radiative cooling of up to −5 W m −2 due to nitrate is seen, with a much smaller global average cooling of −0.05 W m −2 . Significant enhancements in regional cloud condensation nuclei (at 0.1% supersaturation) and cloud droplet number concentrations are also attributed to nitrate, causing an additional global average shortwave cooling of −0.8 W m −2 . Taking into consideration of changes in both longwave and shortwave radiation under all‐sky conditions, the net change in the top of the atmosphere radiative fluxes induced by including nitrate aerosol is −0.7 W m −2 .
54 ENVIRONMENTAL SCIENCES↗
Analytic rate theory of polariton relaxation that explains long polariton lifetime
Hybridization of a molecular exciton with a quantized photon creates a polariton. Despite extensive experimental investigations, the apparent lifetime of the exciton–polariton is not well-understood. For this work, we examined the steady-state population dynamics for a Holstein–Tavis–Cumming Hamiltonian to illuminate the long-term polaritonic dynamics and lifetime of the exciton–polariton in an optical cavity. For a realistic description of polariton relaxation, cavity loss and various exciton decay channels are included in the model. We found that in the presence of weak but finite exciton loss, the apparent lifetime of the lower polariton coincides with the out-of-cavity exciton lifetime and is independent of cavity-matter detuning. This is a simple explanation for the experimentally observed lifetimes for exciton polaritons and theoretically justifies the dark state reservoir hypothesis. Furthermore, if the upper polariton is initially populated, the system reaches the steady state very quickly, leading to single-exponential polariton relaxation. Starting from the lower polariton leads to a longer pre-steady-state time period, leading to double-exponential relaxation. Finally, we considered the effect of site orientational disorders and the exciton frequency disorderers. Under the collective limit, the effects of this disorder can be included in Fermi’s golden rule population dynamics without explicit sampling. For the exciton energy disorders, numerical calculations are needed. Our theoretical framework is applicable to interpret exciton–polariton experiments, especially related to the measured apparent lifetime of polaritons.
Chemical dynamics↗
Novel inverse oxide/metal catalysts for methanol synthesis: impact of oxide–metal interactions and reversible morphological changes
Inverse oxide/metal catalysts have proved to be excellent systems for the generation of methanol by CO 2 hydrogenation or the partial oxidation of methane. These systems can exhibit unique structural and chemical properties due to the nano size of the oxide component and strong oxide–metal interactions. Recent studies for ZnO/Cu, CeO 2 /Cu, TiO 2/ Cu, MgO/Cu, In 2 O 3 /Cu, and In 2 O 3 /Au catalysts have shown large variations in the composition and morphology of the oxide overlayer as a function of temperature and chemical environment. These oxide–metal interfaces are able to react with CO 2 and CH 4 at room temperature, and both reactants have a strong influence on the physical and chemical properties of the catalysts. Under reaction conditions, switches between oxide–metal and metal–metal interfaces can take in the catalyst surface. A dynamic behavior that can be linked to a high selectivity for methanol production over systems such as ZnO/Cu, CeO 2 /Cu and In 2 O 3 /Au. Finally, this type of correlation deserves additional systematic studies since it could be a powerful tool for designing highly efficient catalysts for methanol synthesis.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Structural Basis for Flip-Flop Action of Thiamin Pyrophosphate-Dependent Enzymes Revealed by Human Pyruvate Dehydrogenase
Thiamin pyrophosphate (TPP), the biologically active form of vitamin BI, is a cofactor of enzymes catalyzing reactions involving the cleavage of a carbon-carbon bond adjacent to an oxo group. TPP-dependent enzymes show a common mechanism of TPP activation by: (1) forming the ionic N-H...O(sup -) hydrogen bonding between the N1' atom of the aminopirymidine ring of the coenzyme and intrinsic gamma-carboxylate group of glutamate and (2) imposing an "active" V-conformation that brings the N4' atom of the aminopirymidine to the distance required for the intramolecular C-H.. .N hydrogen bonding with the thiazolium C2 atom. Within these two hydrogen bonds that rapidly exchange protons, protonation of the N1' atom is strictly coordinated with the deprotonation of the 4' -amino group and eventually abstraction of the proton from C2. The human pyruvate dehydrogenase Elp, component of human pyruvate dehydrogenase complex, catalyzes the irreversible decarboxylation of the pyruvate followed by the reductive acetylation of the lipoyl group of dihydrolipoyl acyltransferase. Elp is alpha(sub 2)beta(sub2)-heterotetrameric with a molecular mass of I54 kDa, which has two catalytic sites, each providing TPP and magnesium ion as cofactors and each formed on the interface between the PP and PYR domains. The dynamic nonequivalence of two otherwise chemically equivalent catalytic sites has been observed and the flip-flop mechanism was suggested, according to which two active sites affect each other and in which different steps of the catalytic reaction are performed in each of the sites at any given moment. Based on specific futures of human pyruvate dehydrogenase including rigid and flexible connections between domains that bind the cofactor we propose a mechanistic model for the flip-flop action of this enzyme. We postulate that the dynamic protein environment drives the exchange of tautomers in the 4' -aminopyrimidine ring of the cofactor through a concerted shuttl-like motion of tightly connected domains. The dynamic exchange of those tautomers, in turns, is required during the reactions of pyruvate decarboxylation and reductive acetylation of lipoamide. Thus the shuttle-like motion of the domains is coordinated with the reactions of decarboxylation and acetylation, which are carried out in each of the cofactor sites resulting in a flip-flop action of the enzyme. The structure-derived mechanism of action of human pyruvate dehydrogenase may be likely common for other TPP-dependent enzymes.
Dominiak, Paulina↗
Influence of pump laser fluence on ultrafast myoglobin structural dynamics
High-intensity femtosecond pulses from an X-ray free-electron laser enable pump–probe experiments for the investigation of electronic and nuclear changes during light-induced reactions. On timescales ranging from femtoseconds to milliseconds and for a variety of biological systems, time-resolved serial femtosecond crystallography (TR-SFX) has provided detailed structural data for light-induced isomerization, breakage or formation of chemical bonds and electron transfer. However, all ultrafast TR-SFX studies to date have employed such high pump laser energies that nominally several photons were absorbed per chromophore. As multiphoton absorption may force the protein response into non-physiological pathways, it is of great concern whether this experimental approach allows valid conclusions to be drawn vis-à-vis biologically relevant single-photon-induced reactions. Here we describe ultrafast pump–probe SFX experiments on the photodissociation of carboxymyoglobin, showing that different pump laser fluences yield markedly different results. In particular, the dynamics of structural changes and observed indicators of the mechanistically important coherent oscillations of the Fe–CO bond distance (predicted by recent quantum wavepacket dynamics) are seen to depend strongly on pump laser energy, in line with quantum chemical analysis. Our results confirm both the feasibility and necessity of performing ultrafast TR-SFX pump–probe experiments in the linear photoexcitation regime. We consider this to be a starting point for reassessing both the design and the interpretation of ultrafast TR-SFX pump–probe experiments such that mechanistically relevant insight emerges.
59 BASIC BIOLOGICAL SCIENCES↗
Developing Reaction Chemistry Models from Reactive Molecular Dynamics: TATB
Reactive Molecular Dynamic (RMD) are used to simulate the cook-off chemistry of TATB at a variety of fixed density and fixed temperature conditions. The chemical transformations are monitored using a Coordination Geometry Analysis (CGA) approach which tracks which atom types are bonded to each specific atom. This particularly identifies oxidation state changes that occur during the transformations. Correlations between these different chemical changes are identified using a Non-negative Matrix Factorization (NMF) approach. These identify reduced order chemistry models for the TATB system which contains six components whose concentration profiles are a function of both the temperature and density/pressure. The time histories of these transformations appear to show exponential growth/decay properties that could be fit with Arrhenius rates. These components should form the basis of deflagration rate models for these materials which could then be used in mesoscale simulations to analyze accidental initiation, shock-to-detonation and detonation propagation.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Atom-Specific Probing of Electron Dynamics in an Atomic Adsorbate by Time-Resolved X-Ray Spectroscopy
The electronic excitation occurring on adsorbates at ultrafast timescales from optical lasers that initiate surface chemical reactions is still an open question. Here, in this work, we report the ultrafast temporal evolution of x-ray absorption spectroscopy (XAS) and x-ray emission spectroscopy (XES) of a simple well-known adsorbate prototype system, namely carbon (C) atoms adsorbed on a nickel [Ni(100)] surface, following intense laser optical pumping at 400 nm. We observe ultrafast (~100 fs) changes in both XAS and XES showing clear signatures of the formation of a hot electron-hole pair distribution on the adsorbate. This is followed by slower changes on a few picoseconds timescale, shown to be consistent with thermalization of the complete C/Ni system. Density functional theory spectrum simulations support this interpretation.
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
Chemistry of Sugar Formation in the Gas Phase: Following the Activated Aldehyde
Sugars are produced by living organisms, and are required building blocks for life as we know it, which raises the foundational question of how sugars formed in a prebiotic environment. The abiotic formose reaction produces sugars from formaldehyde, but our understanding of its initiation step remains murky, with chemists invoking the concept of an “activated aldehyde” to seed this reaction. Singlet hydroxycarbenes, high-energy isomers of aldehydes, were recently reported to facilitate sugar formation under cold, nonaqueous conditions relevant to interstellar environments. Here, we generate singlet methylhydroxycarbene ( 1 CH 3 –C̈–OH) from the photodissociation of pyruvic acid and experimentally measure its gas-phase reaction with d 4 -acetaldehyde using multiplexed photoionization mass spectrometry. The C 4 H 4 D 4 O 2 isomer d 4 -acetoin is the sole product, which we kinetically link to the reactant CH 3 –C̈–OH, and attribute to a carbonyl-ene formation mechanism. We see no evidence of 3-hydroxybutanal, the C–H insertion product expected in carbene chemistry. Using automated exploration we calculate stationary points on the potential energy surface and report master equation rate coefficients from T = 20–600 K, providing quantitative kinetics of this fast reaction for use in chemical models. The prereactive complex in this reaction is stabilized by both hydrogen bonding and electrophilic carbene C═O interactions. These effects create a short-range dynamical bottleneck for the reaction besides the long- and midrange barrierless bottlenecks. Combined with recent reports of 1 HC̈OH production from methanol photodissociation and pyruvic acid production in cold irradiated ices, this work provides evidence that singlet hydroxycarbene + aldehyde chemistry is a feasible path to prebiotic sugar formation.
aldehydes↗
Protonation Dynamics of Confined Ethanol–Water Mixtures in H-ZSM-5 from Machine Learning-Driven Metadynamics
Zeolites are indispensable heterogeneous catalysts in industrial chemical processes, valued for their strong Brønsted acidity, well-defined microporous frameworks, and tunable pore structures. Their catalytic activity arises primarily from Brønsted acid sites (BAS), typically present as bridging hydroxyl groups (Si–OH–Al). Under aqueous reaction conditions, these protons interact dynamically with water and alcohol molecules, leading to complex solvation and protonation behavior within confined pores. In this study, we investigate the protonation equilibrium occurring between ethanol and water at the BAS of acidic zeolites under varying hydration levels, i.e., C2H5OH–(H2O)n, n=1–4. Local structure was analyzed through an adaptive-learning global optimization algorithm, while enhanced sampling molecular dynamics simulations with Well-Tempered Metadynamics (WMetaD) and machine learning interatomic potentials (MLPs) provide free-energy surfaces (FES) at variable hydration levels. The results reveal a strong dependence of proton localization on the degree of hydration. At low hydration (1 water molecule), the proton resides predominantly on ethanol; with 2 water molecules, it shifts toward water, and at higher hydration (3 or more water molecules), it becomes extensively delocalized over the water cluster. These findings underscore the critical role of solvation in modulating acid site behavior and suggest that a minimum of three water molecules is necessary to fully stabilize the proton on water within the zeolite framework. This solvation threshold has significant implications for catalytic processes, particularly in biomass conversion reactions where alcohol protonation is a key step in dehydration mechanisms.
machine learning↗
Observational and Modeling Studies of Radiative, Chemical, and Dynamical Interactions in the Earth''s Atmosphere
A 3-dimensional model was developed to support mechanistic studies. The model solves the global primitive equations in isentropic coordinates, which directly characterize diabatic processes forcing the Brewer-Dobson circulation of the middle atmosphere. It's numerical formulation is based on Hough harmonics, which partition horizontal motion into its rotational and divergent components. These computational features, along with others, enable 3D integrations to be performed practically on RISC computer architecture, on which they can be iterated to support mechanistic studies. The model conserves potential vorticity quite accurately under adiabatic conditions. Forced by observed tropospheric structure, in which integrations are anchored, the model generates a diabatic circulation that is consistent with satellite observations of tracer behavior and diabatic cooling rates. The model includes a basic but fairly complete treatment of gas-phase photochemistry that represents some 20 chemical species and 50 governing reactions with diurnally-varying shortwave absorption. The model thus provides a reliable framework to study transport and underlying diabatic processes, which can then be compared against chemical and dynamical structure observed and in GCM integrations. Integrations with the Langley GCM were performed to diagnose feedback between simulated convection and the tropical circulation. These were studied in relation to tropospheric properties controlling moisture convergence and environmental conditions supporting deep convection, for comparison against mechanistic integrations of wave CISK that successfully reproduce the Madden-Julian Oscillation (MJO) of the tropical circulation. These comparisons were aimed at identifying and ultimately improving aspects of the convective simulation, with the objective of recovering a successful simulation of the MJO in the Langley GCM, behavior that should be important to budgets of upper-tropospheric water vapor and chemical species.
Salby, Murry↗
Interplay between disorder, local relaxation, and collective behavior for an ensemble of emitters outside versus inside a cavity
The interplay between collective optical response and molecular static and dynamic disorder is studied using simple effective Hamiltonians for an ensemble of two-level emitters inside and outside a single-mode cavity. We model environmental disorder by randomly modulating the molecular transition frequencies and the coupling between the emitters and the electromagnetic field. We also consider the effects of intermolecular interactions and orientational disorder. We investigate how these effects lead to new features in the steady-state absorption (outside the cavity), transmission spectra (inside the cavity), and the yield of local molecular processes such as a unimolecular reaction. Outside the cavity, the collective behavior is manifested in the linewidth of the steady-state absorption, the emission spectrum, and the local chemical yield. Inside the cavity, however, the collective behavior primarily determines the Rabi splitting. The effects of intermolecular interactions under orientational disorder are also studied. For the most part, for all types of disorder, if we increase disorder, we find a reduction in the collective nature of the molecular response (smaller effective N) and therefore the Rabi splitting contraction occurs with orientational disorder. Furthermore, we find that static disorder is more destructive to collective behavior than dynamic disorder.
74 ATOMIC AND MOLECULAR PHYSICS↗
Ignition of magnesium powders in shock wave induced flows
Ignition of magnesium powders, resulting from an interaction with incident shock wave-induced flows, has been studied. A numerical analysis of particle dynamics and heating is presented and compared with experimental measurements. The induction period is strongly dependent on convective heat transfer and not on chemical reaction rate. Experimentally observed ignition delays were on the order of 100 microns and were inversely dependent on shock strength and initial pressure, directly dependent on particle size and cloud concentration, and independent of oxygen concentration down to 2.3 percent oxygen. Good agreement between experiment and theory was realized.
Fox, T. W.↗
Explosive Event in MON-3 Oxidizer System Resulting from Pressure Transducer Failure
In 2003, a Druck(Registered Trademark) pressure transducer failed catastrophically in a test system circulating nitrogen tetroxide at NASA Johnson Space Center White Sands Test Facility. The cause of the explosion was not immediately obvious since the wetted areas of the pressure transducer were constructed of materials compatible with nitrogen tetroxide. Chemical analysis of the resulting residue and a materials analysis of the diaphragm and its weld zones were used to determine the chain of events that led to the catastrophic failure. Due to excessive dynamic pressure loading in the test system, the diaphragm in the pressure transducer suffered cyclic failure and allowed the silicon oil located behind the isolation diaphragm to mix with the nitrogen tetroxide. The reaction between these two chemicals formed a combination of 2,4-di and 2,4,6-trinitrophenol, which are shock sensitive explosives that caused the failure of the pressure transducer. Further research indicated numerous manufacturers offer similar pressure transducers with silicone oil separated from the test fluid by a thin stainless steel isolation diaphragm. Caution must be exercised when purchasing a pressure transducer for a particular system to avoid costly failures and test system contamination.
Baker, David L.↗
Atomic Dynamics of Multi‐Interfacial Migration and Transformations
Redox-induced interconversions of metal oxidation states typically result in multiple phase boundaries that separate chemically and structurally distinct oxides and suboxides. Directly probing such multi-interfacial reactions is challenging because of the difficulty in simultaneously resolving the multiple reaction fronts at the atomic scale. Using the example of CuO reduction in H 2 gas, a reaction pathway of CuO → monoclinic m-Cu 4 O 3 → Cu 2 O is demonstrated and identifies interfacial reaction fronts at the atomic scale, where the Cu 2 O/m-Cu 4 O 3 interface shows a diffuse-type interfacial transformation; while the lateral flow of interfacial ledges appears to control the m-Cu 4 O 3 /CuO transformation. Together with atomistic modeling, it is shown that such a multi-interface transformation results from the surface-reaction-induced formation of oxygen vacancies that diffuse into deeper atomic layers, thereby resulting in the formation of the lower oxides of Cu 2 O and m-Cu 4 O 3 , and activate the interfacial transformations. In conclusion, these results demonstrate the lively dynamics at the reaction fronts of the multiple interfaces and have substantial implications for controlling the microstructure and interphase boundaries by coupling the interplay between the surface reaction dynamics and the resulting mass transport and phase evolution in the subsurface and bulk.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗