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At least 667 records · Page 37
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

The role of cool-flame fluctuations in high-pressure spray flames, studied using high-speed optical diagnostics and Large-Eddy Simulations

Here this work investigates the low- and high-temperature ignition and combustion processes, applied to the Engine Combustion Network Spray A flame, combining advanced optical diagnostics and large-eddy simulations (LES). Simultaneous high-speed (50 kHz) formaldehyde (CH 2 0) planar laser-induced fluorescence (PLIF) and line-of-sight OH* chemiluminescence imaging were used to measure the low- and high-temperature flame, during ignition as well as during quasi-steady combustion. While tracking the cool flame at the laser sheet plane, the present experimental setup allows detection of distinct ignition spots and dynamic fluctuations of the lift-off length over time, which overcomes limitations for flame tracking when using schlieren imaging. After significant development to improve LES prediction of the low-and high-temperature flame position, both during the ignition processes and quasi-steady combustion, the simulations were analyzed to gain understanding of the mixture variance and how this variance affects formation/consumption of CH 2 0. Analysis of the high-temperature ignition period shows that a key improvement in the LES is the ability to predict heterogeneous ignition sites, not only in the head of the jet, but in shear layers at the jet edge close to the position where flame lift-off eventually stabilizes. The LES analysis also shows concentrated pockets of CH 2 0, in the center of jet and at 20 mm downstream of the injector (in regions where the equivalence ratio is greater than 6), that are of similar length scale and frequency as the experiment (approximately 5–6 kHz). The periodic oscillation of CH 2 0 match the frequency of pressure waves generated during auto-ignition and reflected within the constant-volume vessel throughout injection. The ability of LES to capture the periodic appearance and destruction of CH 2 0 is particularly important because these structures travel downstream and become rich premixed flames that affect soot production.

42 ENGINEERING↗
DOE OSTI2022

The role of radical-radical chain-propagating pathways in the phenyl + propargyl reaction

Well-skipping radical-radical reactions can provide a chain-propagating pathway for formation of polycyclic radicals implicated in soot inception. Here we use controlled pyrolysis in a microreactor to isolate and examine the role of well-skipping channels in the phenyl (C 6 H 5 ) + propargyl (C 3 H 3 ) radical-radical reaction at temperatures of 800-1600 K and pressures near 25 Torr. The temperature and concentration dependence of the closed-shell (C 9 H 8 ) and radical (C 9 H 7 ) products are observed using electron-ionization mass spectrometry. The flow in the reactor is simulated using a boundary layer model employing a chemical mechanism based on recent rate coefficient calculations. Further, comparison between simulation and experiment shows reasonable agreement, within a factor of 3, while suggesting possible improvements to the model. In contrast, eliminating the well-skipping reactions from the chemistry mechanism causes a much larger discrepancy between simulation and experiment in the temperature dependence of the radical concentration, revealing that the well-skipping pathways, especially to form indenyl radical, are significant at temperatures of 1200 K and higher. While most C 9 H 7 forms by well-skipping at 25 Torr, an additional simulation indicates that the wellskipping channels only contribute around 3% of the C 9 H x yield at atmospheric pressure, thus indicating a negligible role of the well-skipping pathways at atmospheric and higher pressures.

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

Visualization of post-detonation fireball flowfields and comparison to CFD modeling

Visualization of flow structures within post-detonation fireballs has been performed for benchmark validation of numerical simulations. Custom pressed PETN explosives with a 12-mm diameter hemispherical form factor were used to produce a spherically symmetric post-detonation flow with low soot yield. Hydroxyl-radical planar laser induce fluorescence (OH-PLIF) was employed to visualize the structure ranging from approximately 10 μs to 35 μs after shock breakout from the explosive pellet. Fireball simulations were performed using the HyBurn Computational Fluid Dynamics (CFD) package. Experimental OH-PLIF results were compared to synthetic OH-PLIF from post-processing of CFD simulations. From the comparison of experimental and synthetic OH-PLIF images, CFD is shown to replicate much of the flow structure observed in the experiments, revealing potential differences in turbulent length scales and OH kinetics. Furthermore, results provide significant advancement in experimental resolution of these harsh turbulent combustion environments and validate physical models thereof.

Detonator↗
DOE OSTI2024

An improved semi-global intrinsic kinetics model for high temperature carbon oxidation

Measurements of the oxidation rates of various forms of carbon (soot, graphite, coal char) have often shown an unexplained attenuation with increasing temperatures in the vicinity of 2000 K, even when accounting for diffusional transport limitations and gas-phase chemical effects (e.g. CO 2 dissociation). With the development of oxy-fuel combustion approaches for pulverized coal utilization with carbon capture, high particle temperatures are readily achieved in sufficiently oxygen-enriched environments. Here, in this work, a new semi-global intrinsic kinetics model for high temperature carbon oxidation is created by starting with a previously developed 5-step mechanism that was shown to reproduce all major known trends in carbon oxidation, except for its high temperature kinetic falloff, and incorporating a recently discovered surface oxide decomposition step. The predictions of this new model are benchmarked by deploying the kinetic model in a steady-state reacting particle code (SKIPPY) and comparing the simulated results against a carefully measured set of pulverized coal char combustion temperature measurements over a wide range of oxygen concentrations in N 2 and CO 2 environments. The results show that the inclusion of the spontaneous surface oxide decomposition reaction step significantly improves predictions at high particle temperatures. Furthermore, the simulations reveal that O atoms released from the oxide decomposition step enhance the radical pool in the near-surface region and within the particle interior itself. Incorporation of literature rates for O and OH reactions with the carbon surface results in a reduction in the predicted radical pool concentrations and a very minor enhancement of the overall carbon oxidation rate.

33 ADVANCED PROPULSION SYSTEMS↗
DOE OSTI2026

Flame stabilization in DME spray flames under engine-relevant conditions characterized by OH* chemiluminescence and formaldehyde laser-induced fluorescence

The transient and quasi-steady flame structures of Dimethyl Ether (DME) fuel sprays, produced by a single-hole injector (Spray D), were investigated using Planar Laser-Induced Fluorescence (PLIF) and chemiluminescence imaging in a constant-volume chamber under Engine Combustion Network (ECN) Spray A conditions (900 K ambient temperature, 60 bar ambient pressure, 1500 bar injection pressure, and 22.8 kg/m 3 ambient density). Low-temperature chemical reaction zones were visualized using formaldehyde (CH 2 O) PLIF with 355 nm excitation, while high-temperature flame regions were captured via chemiluminescence imaging of excited-state hydroxyl radicals (OH*). Both transient and quasi-steady flame structures clearly show the transition from CH 2 O to OH*, highlighting the progression from low- to high-temperature combustion, while the position of the flame is displaced for DME compared to reference hydrocarbon n-dodecane. Homogeneous reactor calculations with detailed chemistry and using adiabatic mixing for initial temperature show that CH 2 O peaks are significantly higher for DME at the same equivalence ratio, with a higher heat-release during the cool-flame regime with respect to the fuel heating value. Thus, the cool-flame dynamic as a precursor to high-temperature combustion and flame stabilization exhibit distinct behavior for DME relative to conventional hydrocarbons, and these phenomena are effectively resolved through the soot-free nature of DME and the high-speed, time-resolved diagnostics.

CH2O laser-induced fluorescence↗
DOE OSTI2025

Molecular Mass Growth Processes to Polycyclic Aromatic Hydrocarbons through Radical–Radical Reactions Exploiting Photoionization Reflectron Time-of-Flight Mass Spectrometry

Polycyclic aromatic hydrocarbons (PAHs) represent critical building blocks in molecular mass growth processes to carbonaceous nanoparticles, referred to as interstellar and circumstellar grains along with soot particles in astrophysical environments and combustion systems, respectively. Recent advancements on elucidating elementary steps to PAHs have utilized reactions of aromatic radicals, resonantly stabilized free radicals, and aliphatic radicals with closed shell hydrocarbons. However, the role of radical–radical reactions (RRRs) leading to PAHs has remained largely unexplored on the molecular level due to preceding experimental challenges in producing sufficiently high number densities of radical reactants for isomer-selective detection of products from bimolecular and termolecular reactions. This Account offers the latest developments in our knowledge on the mechanisms and pathways to PAHs via RRRs probed in a chemical microreactor at temperatures as high as 1600 K. Product preservation in a molecular beam coupled with synchrotron vacuum ultraviolet photoionization reflectron time-of-flight mass spectrometry and photoelectron photoion coincidence spectroscopy enabled isomer-selective detection of PAHs of up to three rings by their photoionization efficiency curves, which were fit with a linear combination of reference curves for identification. Experiments were combined with computational fluid dynamics modeling of the physicochemical processes in the microreactor, as well as high-level electronic structure calculations to reveal the reaction pathways of each system. Six distinct reaction mechanisms were discovered in this work: propargyl addition─benzannulation (PABA), methyl addition─ring expansion (MARE), cyclopentadienyl addition─naphthylization (CPAN), fulvenallenyl addition─cyclization─aromatization (FACA), benzyl addition─aromatization (BAA), and phenyl addition─pentacyclization (PAP). By systematically varying the number of carbon atoms in the radical reactants, molecular mass growth processes involving reactions between radicals with odd numbers of carbon atoms access aromatics carrying one, two, or three six-membered rings, whereas reactions between even- and odd-carbon-numbered radicals produce aromatics combining five- and six-membered rings. Our investigations reveal unconventional cycloadditions on excited state triplet surfaces, additions of radicals to low spin density carbon-centered radicals, spiroaromatic and fulvene-type intermediates, and highly strained bicyclic reaction intermediates, challenging current perceptions of PAH molecular mass growth processes. All of the listed mechanisms, except for FACA, feature endoergic reactions or barriers which lie above the separated reactants and therefore might be central to circumstellar environments of carbon-rich stars and planetary nebulae as their descendants, but they play no role in the gas phase of cold molecular clouds where temperatures as low as 10 K dominate. Altogether, this work provides detailed reaction mechanisms of PAH growth processes, advancing our knowledge of the chemistry of carbonaceous matter in the universe.

Addition reactions↗
DOE OSTI2021

Use of Transmission Electron Microscopy for Analysis of Aerosol Particles and Strategies for Imaging Fragile Particles

For over 25 years, transmission electron microscopy (TEM) has provided a method for the study of aerosol particles with sizes from below the optical diffraction limit to several microns, resolving the particles as well as smaller features. The wide use of this technique to study aerosol particles has contributed important insights about environmental aerosol particle samples and model atmospheric systems. TEM produces an image that is a 2D projection of aerosol particles that have been impacted onto grids and, through associated techniques and spectroscopies, can contribute additional information such as the determination of elemental composition, crystal structure, and 3D particle structures. Soot, mineral dust, and organic/inorganic particles have all been analyzed using TEM and spectroscopic techniques. TEM, however, has limitations that are important to understand when interpreting data including the ability of the electron beam to damage and thereby change the structure and shape of particles, especially in the case of particles composed of organic compounds and salts. In this paper, we concentrate on the breadth of studies that have used TEM as the primary analysis technique. Another focus is on common issues with TEM and cryogenic-TEM. Insights for new users on best practices for fragile particles, that is, particles that are easily susceptible to damage from the electron beam, with this technique are discussed. Tips for readers on interpreting and evaluating the quality and accuracy of TEM data in the literature are also provided and explained.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Biodiesel Ethers: Fatty Acid-Derived Alkyl Ether Fuels as Improved Bioblendstocks for Mixing-Controlled Compression Ignition Engines

In the last 20 years, biodiesel consumption in the United States has swiftly increased to ~2 billion gallons per year as a renewable supplement to fossil fuel. However, further expansion of biodiesel use is currently limited in part by poor cold weather performance, which prevents year-round blending and necessitates blend walls ≤5% v/v. In order to provide a diesel fuel blendstock with improved cold weather performance (cloud point, pour point, and cold filter plug point), while at the same time maintaining other required fuel performance specifications, several biodiesel redox analogues were synthesized and tested. The best performing candidate fuels from this class showed improvement in the derived cetane number (29.3% shorter ignition delay), lower heating value (+4.7 MJ/kg), relative sooting tendency (–7.4 YSI/MJ), and cloud point (15 °C lower) when compared to a B100 biodiesel composed of an identical fatty acid profile. It was observed as a general trend that the reduced form of biodiesel, fatty alkyl ethers (FAEs), shows performance improvements in all fuel property metrics. The suite of improved properties provided by FAEs gives biodiesel producers the opportunity to diversify their portfolio of products derived from lipid and alcohol feedstocks to include long-chain alkyl ethers, a biodiesel alternative with particular applicability for winter weather conditions across the US.

09 BIOMASS FUELS↗
DOE OSTI2021

Probing the Chemical Kinetics of Minimalist Functional Group Gasoline Surrogates

We report surrogate mixtures are routinely used for understanding gasoline fuel combustion in engine simulations. The general trend in surrogate formulation has been to increase the number of fuel components in a mixture to better emulate real fuel properties. Recently, a new surrogate design strategy based on functional group analysis of real gasolines was proposed using a minimal number of species [minimalist functional group (MFG)-approach]. MFG surrogates (having just one or two components) could experimentally capture the ignition delay time (IDT), threshold sooting index, and smoke point of different gasoline fuels with hundreds of components. However, other combustion characteristics were not explored, and kinetic modeling of MFG surrogates was not reported. These aspects are addressed in this paper, where the combustion behavior of MFG surrogates for various gasolines was assessed by simulating IDT, jet-stirred reactor oxidation, and premixed laminar flame speeds using chemical kinetic modeling. MFG simulations were compared with experimental data of the real gasolines as well as with the more complex multicomponent (five to nine species) surrogates. This study reveals that binary MFG surrogate mixtures are capable of accurately simulating the combustion behavior of more complex gasoline fuels with hundreds of components.

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

Experimental and Kinetic Modeling Study of 3-Methyl-2-butenol (Prenol) Oxidation

Longer chain alcohols with 4–5 carbon atoms are attractive alternative fuels as they can be derived from biological sources and since their combustion leads to lower exhaust gas levels of NO x and soot compared to commercial fossil fuels. The auto-ignition behavior of fuels that contain both a hydroxyl group and a C=C double bond in their molecular structure is not well established in the literature. Understanding the influence of these functional groups on the ignition behavior of fuels is critical in the development of tailor-made fuels for advanced combustion engines. In this study, ignition delay times of an unsaturated alcohol, 3-methyl-2-butenol (prenol), are measured using a high-pressure shock tube and a rapid compression machine at pressures of 15 and 30 bar at equivalence ratios of 0.5, 1.0, and 2.0 in “air” in the temperature range 600–1400 K. Furthermore, a detailed kinetic model is developed and validated using the new experimental data in this study. In addition, speciation data in a jet-stirred reactor, ignition delay times, and laminar burning velocities available in the literature were also used to validate the new kinetic model. Fuel flux and sensitivity analyses are performed using this new model to determine the important fuel consumption pathways and critical reactions that affect the reactivity of prenol.

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

Measurements of Intermediate Species in Fuel-Rich Oxidation of Ethylene, Toluene, and n -Decane

Polycyclic aromatic hydrocarbons (PAHs) are important precursors to the formation of soot and are also pollutant emissions from combustion devices, including internal combustion engines. To understand the formation of PAHs, the low-molecular-weight hydrocarbon chemistry leading to their formation needs to be understood. Toward this goal, fuel-rich oxidation of three different hydrocarbons, i.e., ethylene, toluene, and n-decane, has been investigated in an atmospheric pressure flow reactor at varying temperatures (1000–1350 K), equivalence ratios (φ = 3.0–12.0), and residence times of 0.25–1.5 s. The major C 1 to C 7 intermediates, such as methane, acetylene, ethylene, allene, propyne, propylene, vinylacetylene, 1,3-butadiene, cyclopentadiene, benzene, and toluene, were quantified using a gas chromatograph equipped with a flame ionization detector. The experimental tendency of intermediate species formation, e.g., the dependence of temperature, equivalence ratio, and residence time, was similar in ethylene oxidation and n-decane oxidation. The concentrations of intermediate species up to C 4 were higher in ethylene/n-decane oxidation than toluene oxidation, while a nearly equal or larger amount of C5–C7 species was produced in toluene oxidation. The experimental data were compared with modeling results using a detailed chemical kinetic mechanism. The calculated data using the kinetic model were in agreement with the experimental results. Additionally, a comprehensive kinetic analysis on the reaction pathways of each species was conducted to assess the differences in the oxidation chemistry with the change in the structure of hydrocarbons. In particular, in-depth analysis of benzene formation was performed, elucidating that two benzene formation pathways were important in ethylene and n-decane oxidation: (1) H elimination of the 2,4-cyclohexadienyl radical produced from the isomerization of the 2,4-cyclopentadienylmethyl radical, and (2) dehydrogenation of cyclohexadiene produced from reactions of vinyl radical with 1,3-butadiene. In toluene oxidation, it was found that benzene was primarily produced from toluene through the replacement of the methyl group with hydrogen.

30 DIRECT ENERGY CONVERSION↗
DOE OSTI2022

A Conical Intersection Influences the Ground State Rearrangement of Fulvene to Benzene

The rearrangement of fulvene to benzene is believed to play an important role in the formation of soot during hydrocarbon combustion. Previous work has identified two possible mechanisms for the rearrangement-a unimolecular path and a hydrogen-atom-assisted, bimolecular path. Computational results to date have suggested that the unimolecular mechanism faces a barrier of about 74 kcal/mol, which makes it unable to compete with the bimolecular mechanism under typical combustion conditions. This computed barrier is about 10 kcal/mol higher than the experimental value, which is an unusually large discrepancy for modern electronic structure theory. In the present work, we have reinvestigated the unimolecular mechanism computationally, and we have found a second transition state that is approximately 10 kcal/mol lower in energy than the previously identified one and, therefore, in excellent agreement with the experimental value. The existence of two transition states for the same rearrangement arises because there is a conical intersection between the two lowest singlet states which occurs in the vicinity of the reaction coordinates. The two possible paths around the cone on the lower adiabatic surface give rise to the two distinct saddle points. The lower barrier for the unimolecular mechanism now makes it competitive with the bimolecular one, according to our calculations. In support of this conclusion, we have reanalyzed some previous experimental results on anisole pyrolysis, which leads to benzene as a significant product and have shown that the unimolecular and bimolecular mechanisms for fulvene ? benzene must be occurring competitively in that system. Finally, we have identified that similar conical intersections arise during the isomerizations of benzofulvene and isobenzofulvene to naphthalene.

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

Comprehensive Kinetics on the C 7 H 7 Potential Energy Surface under Combustion Conditions

The automated kinetics workflow code, KinBot, was used to explore and characterize the regions of the C 7 H 7 potential energy surface that are relevant to combustion environments and especially soot inception. We first explored the lowest-energy region, which includes the benzyl, fulvenallene + H, and cyclopentadienyl + acetylene entry points. We then expanded the model to include two higher-energy entry points, vinylpropargyl + acetylene and vinylacetylene + propargyl. The automated search was able to uncover the pathways from the literature. In addition, three important new routes were discovered: a lower-energy pathway connecting benzyl with vinylcyclopentadienyl, a decomposition mechanism from benzyl that results in side-chain hydrogen atom loss to produce fulvenallene + H, and shorter and lower energy routes to the dimethylene-cyclopentenyl intermediates. We systematically reduced the extended model to a chemically relevant domain composed of 63 wells, 10 bimolecular products, 87 barriers, and 1 barrierless channel and constructed a master equation using the CCSD(T)-F12a/cc-pVTZ//ωB97X-D/6-311++G(d,p) level of theory to provide rate coefficients for chemical modeling. Our calculated rate coefficients show excellent agreement with measured ones. We also simulated concentration profiles and calculated branching fractions from the important entry points to provide an interpretation of this important chemical landscape.

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 OSTI2025

Identification of the Elusive Methyl-Loss Channel in the Crossed Molecular Beam Study of Gas-Phase Reaction of Dicarbon Molecules (C 2 ; X 1 Σ g + /a 3 Π u ) with 2-Methyl-1,3-butadiene (C 5 H 8 ; X 1 A')

The crossed molecular beams technique was utilized to explore the reaction of dicarbon C 2 (X 1 Σ g + /a 3 Π u ) with 2-methyl-1,3-butadiene (isoprene, CH 2 C(CH 3 )CHCH 2 ; X 1 A') at a collision energy of 28 ± 1 kJ mol⁻¹ using a supersonic dicarbon beam generated via photolysis (248 nm) of helium-seeded tetrachloroethylene (C 2 Cl 4 ). Here, experimental data combined with previous ab initio calculations provide evidence of the detection of the hitherto elusive methyl elimination channels leading to acyclic resonantly stabilized hexatetraenyl radicals: 1,2,4,5-hexatetraen-3-yl (CH 2 CC•CHCCH 2 ) and/or 1,3,4,5-hexatetraen-3-yl (CH 2 CHC•CCCH 2 ). These pathways are exclusive to the singlet potential energy surface, with the reaction initiated by the barrierless addition of dicarbon to one of the carbon-carbon double bonds in the diene. In combustion systems, both hexatetraenyl radicals can isomerize to the phenyl radical (C 6 H 5 ) through a hydrogen atom assisted isomerization – the crucial reaction intermediate and molecular mass growth species step toward the formation of polycyclic aromatic hydrocarbons (PAHs) and soot.

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

Sensitivity of Carbonaceous Aerosol Properties to the Implementation of a Dynamic Aging Parameterization in the Regional Climate Model RegCM

Freshly emitted soot is hydrophobic, but condensation of secondary aerosols and coagulation with other particles modify its hygroscopic optical properties. This conversion is referred to as “aerosol aging.” Many climate models represent this aging process with a fixed aging time scale, whereas in reality, it is a dynamic process that depends on environmental conditions. Here, we implement a dynamic aging parameterization scheme in the regional climate model RegCM4 in place of the fixed aging timescale of 1.15 days (~27.6 h) and examine its impact on the aerosol life cycle over the Indian subcontinent. The conversion from hydrophobic to hydrophilic aerosol is usually lower than 27.6 h over the entire landmass and lower than 10 h over the polluted Indo-Gangetic Basin (IGB), with seasonal variability. Due to the implementation of the dynamic aging scheme, the column burden and surface mass concentration of carbonaceous aerosols increase during the drier season (December–February) when washout is negligible. The burden is reduced during the wet season (June–September) due to a more efficient washout except over the IGB, where a reduction in precipitation as a result of radiative feedbacks increases the aerosol concentrations. Over the polluted IGB, surface dimming increases due to the dynamic aging scheme, with the top of the atmosphere forcing remaining mostly unchanged. As a result, atmospheric heating increases by at least 1.2 W/m 2 . Our results suggest that climate models should incorporate dynamic aging for a more realistic representation of aerosol simulations, especially in highly polluted regions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Prediction of organic homolytic bond dissociation enthalpies at near chemical accuracy with sub-second computational cost

Bond dissociation enthalpies (BDEs) of organic molecules play a fundamental role in determining chemical reactivity and selectivity. However, BDE computations at sufficiently high levels of quantum mechanical theory require substantial computing resources. In this paper, we develop a machine learning model capable of accurately predicting BDEs for organic molecules in a fraction of a second. We perform automated density functional theory (DFT) calculations at the M06-2X/def2-TZVP level of theory for 42,577 small organic molecules, resulting in 290,664 BDEs. A graph neural network trained on a subset of these results achieves a mean absolute error of 0.58 kcal mol-1 (vs DFT) for BDEs of unseen molecules. We further demonstrate the model on two applications: first, we rapidly and accurately predict major sites of hydrogen abstraction in the metabolism of drug-like molecules, and second, we determine the dominant molecular fragmentation pathways during soot formation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗