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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 OSTI2022

Molecular Polaritonics: Chemical Dynamics Under Strong Light–Matter Coupling

Chemical manifestations of strong light–matter coupling have recently been a subject of intense experimental and theoretical studies. Here we review the present status of this field. Section 1 is an introduction to molecular polaritonics and to collective response aspects of light–matter interactions. Section 2 provides an overview of the key experimental observations of these effects, while Section 3 describes our current theoretical understanding of the effect of strong light–matter coupling on chemical dynamics. A brief outline of applications to energy conversion processes is given in Section 4. Pending technical issues in the construction of theoretical approaches are briefly described in Section 5. Finally, the summary in Section 6 outlines the paths ahead in this exciting endeavor.

Chemistry↗
DOE OSTI2025

An iterative dynamic chemical stiffness removal method for reacting flow simulations

Abstract An iterative dynamic chemical stiffness removal method (IDCSR) based on quasi-steady-state approximation (QSSA) is proposed. The IDCSR method is built on a previously developed non-iterative method which has proved to work well for small timestep sizes. A novel iterative procedure is designed in IDCSR to enable explicit time integration of stiff chemistry at relatively large timestep sizes relevant to practical reacting flow simulations. The effectiveness of the iterative procedure is first demonstrated with a toy problem and homogeneous auto-ignition with fixed integration step sizes, showing that larger timestep sizes can be allowed for explicit time integration using IDCSR compared with the previous non-iterative method. IDCSR is then compared with existing explicit chemistry solvers for simulations of homogeneous auto-ignition and shows similar or lower computational cost but significantly higher accuracy across a wide range of timestep sizes. IDCSR is further combined with an automatic adaptive time-stepping scheme for simulations of 0-D homogeneous auto-ignition and a 2-D laminar lifted n -dodecane jet flame. For the 0-D auto-ignition simulations, IDCSR is shown to reduce both the error (by 43%–90%) and computational cost (by 6–15 times) compared with existing explicit solvers, while achieving speed-up factors of up to 400 compared with VODE for a wide range of timestep sizes and reaction mechanisms. For the 2-D jet flame simulations, speed-up factors of 15 and 31 for chemistry integration, and 5 and 9 for overall simulation, are achieved by IDCSR compared with CVODE with and without analytic Jacobian, respectively.

Xu, Chao (ORCID:0000000153074159)↗
DOE OSTI2024

UQ4QM: Uncertainty Quantification for Quantum Materials (Chemical Dynamics Initiative Final Report)

The Uncertainty Quantification for Quantum Materials (UQ4QM) LDRD project focused on developing solutions for strategic two project areas the Chemical Dynamics Initiative (CDi) Use Case 3. This included data-driven approaches toward understanding heterogeneous data, such as multi-fidelity data or data with unknown spatial or temporal perturbations. The applications were varied but the project aims pursued solutions which were amenable to common UQ approaches in order to maximize impact.

36 MATERIALS SCIENCE↗
DOE OSTI2024

2D IR Microscopy—Technology for Visualizing Chemical Dynamics in Heterogeneous Environments (Final Technical Report)

The primary focus of this project was the design, prototype, and demonstration of a 2D IR microscope. The start date of this project was July 15, 2016 and the project end date was July 14, 2022. In the early years of this project our team designed, prototyped, and completely integrated a homebuilt microscope head with our high-repetition rate 2D IR spectrometer. Once in place our research team focused on characterizing the 2D IR microscope and using it to investigate model systems relevant to energy technologies. As part of this process, we identified two initial chemical systems to use to further develop 2D IR imaging modalities. The first chemical system developed was a room temperature ionic liquid (RTIL) electrolyte system and the second chemical system was a mixture of carbonates and salts developed as a battery electrolyte system. The completion of this project resulted in the full characterization of chemical dynamics in a bulk RTIL system and the demonstration of 2D IR imaging across the RTIL cast as a microdroplet in silicon oil. In addition, we explored the liquid structures and dynamics of organic carbonate mixtures from the vantage point of the vibrational probe, methyl thiocyanate. By the end of the project, we had moved toward in-depth studies of the organic carbonate mixtures.

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

Experimental and computational investigation into the hydrodynamics and chemical dynamics of laser ablation aluminum plasmas

Laser ablation plasma chemistry is governed by a complex interplay between hydrodynamic plasma-gas mixing processes, thermodynamics, and rapid high-temperature chemical reactions. Here, in this work, we investigate the gas-phase oxidation chemistry of ns-laser ablation aluminum plasmas in air using optical spectroscopy combined with advanced multi-physics modeling. Experimental measurements demonstrate the formation of AlO in the plasma plume as early as 1 μs while computational results reveal that several Al x O y species are distributed in the periphery of the plume at even earlier times (<20 ns) in the presence of large temperature gradients and strong shockwaves. Interactions with the ablation crater during rapid plume expansion are shown to initiate vortex formation, followed by mixing dynamics that work to pull AlO into the vortices to react with gas-phase Al to form Al 2 O. Oxygen and several aluminum oxides are simultaneously pulled up through the stem of the fireball, encouraging further intermixing between reacting species and enhanced molecular formation. This work concludes that chemical dynamics in laser ablation plasmas is driven by diffusion processes, concentration gradients, and plume hydrodynamics while strong shockwaves generated during laser ablation do not impede chemical reactions.

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

Characterizing coherences in chemical dynamics with attosecond time-resolved x-ray absorption spectroscopy

Coherence can drive wave-like motion of electrons and nuclei in photoexcited systems, which can yield fast and efficient ways to exert materials’ functionalities beyond the thermodynamic limit. The search for coherent phenomena has been a central topic in chemical physics although their direct characterization is often elusive. Here, we highlight recent advances in time-resolved x-ray absorption spectroscopy (tr-XAS) to investigate coherent phenomena, especially those that utilize the eminent light source of isolated attosecond pulses. The unparalleled time and state sensitivities of tr-XAS in tandem with the unique element specificity render the method suitable to study valence electronic dynamics in a wide variety of materials. The latest studies have demonstrated the capabilities of tr-XAS to characterize coupled electronic–structural coherence in small molecules and coherent light–matter interactions of core-excited excitons in solids. Furthermore, we address current opportunities and challenges in the exploration of coherent phenomena, with potential applications for energy- and bio-related systems, potential crossings, strongly driven solids, and quantum materials, and so with the ongoing developments in both theory and light sources, tr-XAS holds great promise for revealing the role of coherences in chemical dynamics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2000

Dynamic-Chemical Coupling of the Upper Troposphere and Lower Stratosphere Region

The importance of the interaction of chemistry and dynamics in the upper troposphere and lower stratosphere for chemical species like ozone is investigated using two chemistry-climate models. Species emitted in the upper troposphere, like NOx (=NO+NO2) by lightning or aircraft, have the chance to be transported into the lowermost stratosphere. Trajectory calculations suggest that the main transport pathway runs via the Inter Tropical Convergence Zone, across the tropical tropopause and then to higher latitudes, i.e. into the lowermost stratosphere. Longer lifetimes of NOx in the lower stratosphere yield an accumulation of NO. there, which feeds back on upper troposphere chemistry. This effect has been estimated for lightning NO. emissions and reveals a contribution of at least 25% to 40% to the total northern hemisphere mid-latitude lightning increase of either NOx and ozone.

Grewe, Volker↗
NASA NTRS1975

A three-dimensional dynamical-chemical model of atmospheric ozone

A three-year integration of a global three-dimensional model including dynamics and simple photochemistry is used to predict ozone. Good agreement with observation is obtained for stratospheric motion patterns, meridional circulations, ozone density as a function of height and latitude, eddy transports of ozone, surface destruction of ozone, and correlations of ozone with other variables. The annual cycle of columnar ozone in high latitudes is present, but at a smaller amplitude than observed. Vertical transport of ozone downward from the main generation level at 30 km is accomplished primarily by small-scale eddy diffusion between 20 and 30 km and again near the ground; large-scale vertical transport dominates in between. The model predicts a secondary maximum in ozone mixing ratio at 45 km somewhat equatorward of the winter polar-night zone. This feature, recently observed from satellite measurements, is thought to be caused by the temperature dependence of reaction rates in the Chapman scheme. The principal deficiency of the model is an underprediction of the spring ozone concentration in high latitudes in the lower stratosphere.

Cunnold, D.↗
DOE OSTI2025

Shake-Down Spectroscopy as State- and Site-Specific Probe of Ultrafast Chemical Dynamics

Tracking the multifarious ultrafast electronic and structural changes occurring in a molecule during a photochemical transformation is a challenging endeavor that benefits from recent experimental and computational progress in time-resolved techniques. Measurements of valence electronic states, which provide a global picture of the bonding structure of the molecule, and core electronic states, which provide insight into the local environment, traditionally require different approaches and are often studied separately. Here, we demonstrate that X-ray pulses from a seeded free-electron laser (FEL) enable the measurement of high-resolution, time-resolved X-ray photoelectron spectra (XPS) that capture weak satellite states resulting from shake-down processes in a valence-excited molecule. This approach effectively combines the advantages of both valence- and core-state investigations. We applied this method to investigate photoexcited CS2 molecules, where the role of internal conversion (IC) and intersystem crossing (ISC) in determining the predissociation dynamics is controversial. We present XPS spectra from photoexcited CS2, obtained at the FERMI FEL. High-resolution measurements, compared to the corresponding spectra obtained from accurate multireference quantum chemical calculations, reveal that shake-down satellite channels are highly sensitive to both valence electronic and geometric changes. Previous studies of the predissociation dynamics have led to uncertain assignments of the branching between singlet and triplet excited states. We derive a propensity rule that demonstrates the spin-selectivity of the shake-downs. This selectivity allows us to unequivocally assign contributions from the bright and dark singlet excited states, with populations tracked along the predissociation dynamic pathway.

Thompson, Henry J. [Univ. of Southampton (United K↗
NASA NTRS1982

Recent theoretical chemical dynamics at Rochester in the paths of Joseph O. Hirschfelder

A review of recent theoretical studies of gas-phase molecular rate processes, including various effects of laser radiation, is presented in the context of the extensive and influential work of Joseph O. Hirschfelder during the past half-century. The topics addressed are energy transfer, chemical reactions, unimolecular dissociation, transition states, and bound-continuum interactions.

George, T. F.↗
DOE OSTI2024

Exploring the chemical dynamics of phenanthrene (C 14 H 10 ) formation via the bimolecular gas-phase reaction of the phenylethynyl radical (C 6 H 5 CC) with benzene (C 6 H 6 )

The exploration of the fundamental formation mechanisms of polycyclic aromatic hydrocarbons (PAHs) is crucial for the understanding of molecular mass growth processes leading to two- and three-dimensional carbonaceous nanostructures (nanosheets, graphenes, nanotubes, buckyballs) in extraterrestrial environments (circumstellar envelopes, planetary nebulae, molecular clouds) and combustion systems. While key studies have been conducted exploiting traditional, high-temperature mechanisms such as the hydrogen abstraction–acetylene addition (HACA) and phenyl addition–dehydrocyclization (PAC) pathways, the complexity of extreme environments highlights the necessity of investigating chemically diverse mass growth reaction mechanisms leading to PAHs. Employing the crossed molecular beams technique coupled with electronic structure calculations, we report on the gas-phase synthesis of phenanthrene (C 14 H 10 )—a three-ring, 14π benzenoid PAH—via a phenylethynyl addition–cyclization–aromatization mechanism, featuring bimolecular reactions of the phenylethynyl radical (C 6 H 5 CC, X 2 A 1 ) with benzene (C 6 H 6 ) under single collision conditions. The dynamics involve a phenylethynyl radical addition to benzene without entrance barrier leading eventually to phenanthrene via indirect scattering dynamics through C 14 H 11 intermediates. The barrierless nature of reaction allows rapid access to phenanthrene in low-temperature environments such as cold molecular clouds which can reach temperatures as low as 10 K. Furthermore, this mechanism constitutes a unique, low-temperature framework for the formation of PAHs as building blocks in molecular mass growth processes to carbonaceous nanostructures in extraterrestrial environments thus affording critical insight into the low-temperature hydrocarbon chemistry in our universe.

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

A Chemical Dynamics Study of the Reaction of the Methylidyne Radical (CH, X 2 Π) with Dimethylacetylene (CH 3 CCCH 3 , X 1 A 1g )

The gas-phase reaction of the methylidyne (CH; X 2 Π) radical with dimethylacetylene (CH 3 CCCH 3 ; X 1 A 1g ) was studied at a collision energy of 20.6 kJ mol -1 under single collision conditions with experimental results merged with ab initio calculations of the potential energy surface (PES) and ab initio molecule dynamics (AIMD) simulations. Here, the crossed molecular beams experiment reveals that the reaction proceeds barrierless via indirect scattering dynamics through long-lived C 5 H 7 reaction intermediate(s) ultimately dissociating to C 5 H 6 isomers along with atomic hydrogen with atomic hydrogen predominantly released from the methyl groups as verified by replacing the methylidyne with the D1-methylidyne reactant. AIMD simulations reveal that the reaction dynamics are statistical leading predominantly to p28 (1-methyl-3-methylene-cyclopropene, 13 %) and p8 (1-penten-3-yne, 81 %) plus atomic hydrogen with a significant amount of available energy being channeled into the internal excitation of the polyatomic reaction products.

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

Development and application of ReaxFF methodology for understanding the chemical dynamics of metal carbonates in aqueous solutions

A new ReaxFF reactive force field has been developed for metal carbonate systems including Na + , Ca 2+ , and Mg 2+ cations and the CO 3 2– anion. This force field is fully transferable with previous ReaxFF water and water/electrolyte descriptions. The Me–O–C (Me = metal) three-body valence angle parameters and Me–C non-reactive parameters of the force field have been optimized against quantum mechanical calculations including equations of state, heats of formation, heats of reaction, angle distortions and vibrational frequencies. The new metal carbonate force field has been validated using molecular dynamics simulations to study the solvation and reactivity of metal and carbonate ions in water at 300 K and 700 K. The coordination radius and self-diffusion coefficient show good consistency with existing experimental and simulation results. The angular distribution analysis explains the structural preference of carbonate ions to form carbonates and bicarbonates, where Na + predominantly forms carbonates due to weaker angular strain, while Ca 2+ and Mg 2+ prefer to form bicarbonate monodentate in nature. Residence time distribution analyses on different systems reveal the role of ions in accelerating and decelerating the dynamics of water and carbonate ions under different thermodynamic conditions. The formation and dissolution of bicarbonates and carbonates in solution were explored on the basis of the protonation capability in different systems. Here, the nucleation phenomenon of metal carbonates at ambient and supercritical conditions is explained from the perspective of cluster formation over time: Ca 2+ ions can form prenucleation clusters at ambient temperature but show saturation with increasing temperature, whereas Na + and Mg 2+ ions show a rapid increase in cluster size and amount upon increasing time and temperature.

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

Elucidating the chemical dynamics of the elementary reactions of the 1-propynyl radical (CH 3 CC; X 2 A 1 ) with 2-methylpropene ((CH 3 ) 2 CCH 2 ; X 1 A 1 )

Exploiting the crossed molecular beam technique, we studied the reaction of the 1-propynyl radical (CH 3 CC; X 2 A 1 ) with 2-methylpropene (isobutylene; (CH 3 ) 2 CCH 2 ; X 1 A 1 ) at a collision energy of 38 ± 3 kJ mol –1 . The experimental results along with ab initio and statistical calculations revealed that the reaction has no entrance barrier and proceeds via indirect scattering dynamics involving C 7 H 11 intermediates with lifetimes longer than their rotation period(s). The reaction is initiated by the addition of the 1-propynyl radical with its radical center to the π-electron density at the C1 and/or C2 position in 2-methylpropene. Further, the C 7 H 11 intermediate formed from the C1 addition either emits atomic hydrogen or undergoes isomerization via [1,2-H] shift from the CH 3 or CH 2 group prior to atomic hydrogen loss preferentially leading to 1,2,4-trimethylvinylacetylene (2-methylhex-2-en-4-yne) as the dominant product. The molecular structures of the collisional complexes promote hydrogen atom loss channels. RRKM results show that hydrogen elimination channels dominate in this reaction, with a branching ratio exceeding 70%. Since the reaction of the 1-propynyl radical with 2-methylpropene has no entrance barrier, is exoergic, and all transition states involved are located below the energy of the separated reactants, bimolecular collisions are feasible to form trimethylsubstituted 1,3-enyne (p1) via a single collision event even at temperatures as low as 10 K prevailing in cold molecular clouds such as G+0.693. As a result, the formation of trimethylsubstituted vinylacetylene could serve as the starting point of fundamental molecular mass growth processes leading to di- and trimethylsubstituted naphthalenes via the HAVA mechanism.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗