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NASA NTRS2014

Additive Construction using Basalt Regolith Fines

Planetary surfaces are often covered in regolith (crushed rock), whose geologic origin is largely basalt. The lunar surface is made of small-particulate regolith and areas of boulders located in the vicinity of craters. Regolith composition also varies with location, reflecting the local bedrock geology and the nature and efficiency of the micrometeorite-impact processes. In the lowland mare areas (suitable for habitation), the regolith is composed of small granules (20 - 100 microns average size) of mare basalt and volcanic glass. Impacting micrometeorites may cause local melting, and the formation of larger glassy particles, and this regolith may contain 10-80% glass. Studies of lunar regolith are traditionally conducted with lunar regolith simulant (reconstructed soil with compositions patterned after the lunar samples returned by Apollo). The NASA Kennedy Space Center (KSC) Granular Mechanics & Regolith Operations (GMRO) lab has identified a low fidelity but economical geo-technical simulant designated as Black Point-1 (BP-1). It was found at the site of the Arizona Desert Research and Technology Studies (RATS) analog field test site at the Black Point lava flow in adjacent basalt quarry spoil mounds. This paper summarizes activities at KSC regarding the utilization of BP-1 basalt regolith and comparative work with lunar basalt simulant JSC-1A as a building material for robotic additive construction of large structures. In an effort to reduce the import or in-situ fabrication of binder additives, we focused this work on in-situ processing of regolith for construction in a single-step process after its excavation. High-temperature melting of regolith involves techniques used in glassmaking and casting (with melts of lower density and higher viscosity than those of metals), producing basaltic glass with high durability and low abrasive wear. Most Lunar simulants melt at temperatures above 1100 C, although melt processing of terrestrial regolith at 1500 C is not uncommon. These temperatures are achievable by laser heating or by using solar concentrators. Similar to volcanic magma, the cooling rate determines the crystallite size - slower cooling develops larger crystals, and rapid quenching can result in fully amorphous glass.

Additive↗

DOE OSTI2025

Single Crystalline Na 0.67 Ni 0.33 Mn 0.67 O 2 Positive Electrode Material via Molten Salt Synthesis for Sodium Ion Batteries

P2-layered Na 0.67 Ni 0.33 Mn 0.67 O 2 (NNMO) has emerged as a promising positive electrode material for sodium ion batteries due to its appealing electrochemical properties. Synthesis of polycrystalline NNMO (PC-NNMO) materials through conventional calcination of solid precursors remains the prevailing method, where heating occurs in a dry environment with air or O 2 . On the other hand, the molten salt method, where precursors are submerged in molten salt medium during calcination, emerged in recent years to be a scalable technique for more controlled crystal growth and uniform morphology in a variety of materials. Here, we utilize the molten salt method to synthesize single crystalline NNMO (SC-NNMO) materials with enhanced electrochemical properties. The SC-NNMO material exhibits an initial specific discharge capacity of 95 mAh g –1 at a 0.1C rate, retaining approximately 88.5% of its capacity after 100 cycles over a wide voltage range of 2.0–4.2 V. Furthermore, SC-NNMO maintains a capacity retention of 83.9% after 300 cycles at a 1C rate compared to 66.6% for PC-NNMO, indicating excellent long-term cycling stability. This stability is further confirmed by the performance of an SC-NNMO//hard carbon full cell, which retains 90.3% of its capacity after 200 cycles at 1C within a voltage window of 1.9–4.1 V. The enhancement in stability of the SC-NNMO sample is attributed to the single crystalline structure suppressing the undesired P2–O2 phase transition at high voltage. This study also presents an easy, efficient, and straightforward molten salt process for SC-NNMO material synthesis, offering valuable insights into the potential application of such methodology for the large-scale, cost-effective production of various sodium-layered transition metal oxide positive electrode materials for SIBs.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

DOE OSTI2024

T-Type Modular DC Circuit Breaker (T-Breaker) for Future DC Networks

The developed T-Type Modular DC Circuit Breaker (T-Breaker) technology offers an all-in-one solution to challenges in DC networks. This includes swift fault detection and protection, power transient stability, and power quality improvement, achieved through the utilization of wide bandgap (WBG) power semiconductors and energy storage devices. The T-Breaker not only facilitates rapid fault current detection and interruption but also implements fault current limiting through active insertion of storage devices or by operating WBG devices in the saturation region. Additionally, with the assistance of energy storage devices, potential overvoltage issues on power devices induced by control signal misalignment can be mitigated. The T-Breaker can be regulated to perform shunt current injection/absorption using the vertical arm and series voltage insertion via the horizontal arm, thereby enhancing DC system stability during voltage or load power fluctuation transients. The OSU team and Raytheon team actively worked together on designing, fabricating, assembling, and testing of two T-Breaker prototypes. The first prototype is rated at 1 kV, 500 A with half-bridge (unipolar) structure to validate the T-Breaker concept. The second prototype is rated at 20 kV, 50 A with full-bridge (bipolar) topology which can reach an efficiency of 99.977%, realize a power density of 60.2 MW/m3, and eliminate the 500-A fault current with a fault response time of around 20 µs. The prototypes show great feasibility of adopting this technology in multiple applications including electrified aircraft, super charging stations, data centers, etc.

24 POWER TRANSMISSION AND DISTRIBUTION↗

NASA NTRS2004

NASA GEOS-3/TRMM Re-analysis: Capturing Observed Tropical Rainfall Variability in Global Analysis for Climate Research

Understanding climate variability over a wide range of space-time scales requires a comprehensive description of the earth system. Global analyses produced by a fixed assimilation system (i.e., re-analyses) - as their quality continues to improve - have the potential of providing a vital tool for meeting this challenge. But at the present time, the usefulness of re-analyses is limited by uncertainties in such basic fields as clouds, precipitation, and evaporation - especially in the tropics, where observations are relatively sparse. Analyses of the tropics have long been shown to be sensitive to. the treatment of cloud precipitation processes, which remains a major source of uncertainty in current models. Yet, for many climate studies it is crucial that analyses can accurately reproduce the observed rainfall intensity and variability since a small error of 1 mm/d in surface rain translates into an error of approx. 30 W/sq m in energy (latent heat) flux. Currently, discrepancies between the observed and analyzed monthly-mean rain rates averaged to 100 km x 100 km resolution can exceed 4 mm/d (or 120 W/sq m ), compared to uncertainties in surface radiative fluxes of approx. 10-20 W/sq m . Improving precipitation in analyses would reduce a major source of uncertainty in the global energy budget. Uncertainties in tropical precipitation have also been a major impediment in understanding how the tropics interact with other regions, including the remote response to El Nino/Southern Oscillation (ENSO) variability on interannual time scales, the influence of Madden-Julian Oscillation (MJO) and monsoons on intraseasonal time scales. A global analysis that can replicate the observed precipitation variability together with physically consistent estimates of other atmospheric variables provides the key to breaking this roadblock. NASA Goddard Space Flight Center has been exploring the use of satellite-based microwave rainfall measurements in improving global analyses and has recently produced a multi-year, 1 x 1 TRMM re-analysis , which assimilates 6-hourly TMI and SSM/I surface rain rates over tropical oceans using a ID variational continuous assimilation (VCA) procedure in the GEOS-3 global data assimilation system. The analysis period extends from 1 November 1997 through 3 1 December 2002. The goal is to produce a multi-year global analysis that is dynamically consistent with available tropical precipitation observations for the community to assess its utility in climate applications and identify areas for further improvements. A distinct feature of the GEOS-3RRMh4 re-analysis is that its precipitation analysis is not derived from a short-term forecast (as done in most operational systems) but is given by a time- continuous model integration constrained by precipitation observations within a 6-h analysis window, while the wind, temperature, and pressure fields are allowed to directly respond to the improved precipitation and associated latent heating structures within the same analysis window. In this talk, I will assess the impact VCA precipitation assimilation on analyses of climate signals ranging from a few weeks to interannual time scales and compare results against other operational and reanalysis products.

Hou, Arthur Y.↗

NASA NTRS2010

Physical and Electrical Characterization of Aluminum Polymer Capacitors

Conductive polymer aluminum capacitor (PA capacitor) is an evolution of traditional wet electrolyte aluminum capacitors by replacing liquid electrolyte with a solid, highly conductive polymer. On the other hand, the cathode construction in polymer aluminum capacitors with coating of carbon and silver epoxy for terminal connection is more like a combination of the technique that solid tantalum capacitor utilizes. This evolution and combination result in the development of several competing capacitor construction technologies in manufacturing polymer aluminum capacitors. The driving force of this research on characterization of polymer aluminum capacitors is the rapid progress in IC technology. With the microprocessor speeds exceeding a gigahertz and CPU current demands of 80 amps and more, the demand for capacitors with higher peak current and faster repetition rates bring conducting polymer capacitors to the center o( focus. This is because this type of capacitors has been known for its ultra-low ESR and high capacitance. Polymer aluminum capacitors from several manufacturers with various combinations of capacitance, rated voltage, and ESR values were obtained and tested. The construction analysis of the capacitors revealed three different constructions: conventional rolled foil, the multilayer stacking V-shape, and a dual-layer sandwich structure. The capacitor structure and its impact on the electrical characteristics has been revealed and evaluated. A destructive test with massive current over stress to fail the polymer aluminum capacitors reveals that all polymer aluminum capacitors failed in a benign mode without ignition, combustion, or any other catastrophic failures. The extraordinary low ESR (as low as 3 mOMEGA), superior frequency independence reported for polymer aluminum capacitors have been confirmed. For the applications of polymer aluminum capacitors in space programs, a thermal vacuum cycle test was performed. The results, as expected, show no impact on the electrical characteristics of the capacitors. The breakdown voltage of polymer capacitors has been evaluated using a steady step surge test. Initial results show the uniform distribution in the breakdown voltage for polymer aluminum capacitors. Polymer aluminum capacitors with a combination of very high capacitance, extraordinary low ESR, excellent frequency stability, and non-ignite benign failure mode make it a niche fit in space applications for both today and future. Polymer capacitors are apparently also the best substitutes of the currently used MnO2-based tantalum capacitors in the low voltage range. However, some critical aspects are still to be addressed in the next phase of the investigation for PA capacitors. These include the long term reliability test of 125 C dry life and 85 C/85%RH humidity, the failure mechanism and de-rating, the radiation tolerance, and the high temperature performance. All of the above requires the continuous NEPP funding and support.

Liu, David (Donghang)↗

NASA NTRS2018

Development of Large Bandgap Materials Using Reactive Growth in Al-SI Eutectic for Optical and RF Applications

Carbon was utilized as reactive element to modify the microstructure using forced mixing during crystallization of the Al-Si alloy by rotation and stirring. We nucleated the material on SiC substrates while the Al-Si melt was rotated with a speed of 30rpm in a graphite crucible. Several experiments were performed and parameters such as time of mixing, soaking temperature, rotation rate of the substrate and rate of cooling during the solidification was changed. We observed dendrite and cell morphologies during the solidification of rotating melt. The microstructure was characterized by optical microscopy and SEM-EDX and compositional spectroscopy. The effect of carbon impurities was studied on the solidifying microstructure. When we used the longer soak time of the melt in presence of carbon impurities we observed the destruction of dendritic morphology and the formation of cellular and colony structures. Similar approach has been used for Ga2O3, a novel large bandgap material also.

Singh, N. B.↗

DOE OSTI2025

Semi‐Continuous Ex Situ Carbon Dioxide Mineralization in Produced Water for Calcite Production

ABSTRACT The mineralization of carbon dioxide (CO 2 ) to stable carbonate products is a desirable process for carbon capture utilization and storage (CCUS). However, improving the process economics through creative use of available reactants is necessary to develop a scalable mineralization process. This study details the development of a semi‐continuous CO 2 mineralization process that uses flue gas as a point CO 2 source, produced water (PW) as an alkaline source of Ca 2+ , and NaOH effluent (potentially sourced from integration with the chlor‐alkali process. Operating at a controlled pH allowed for both complete reaction of available Ca 2+ (100% carbonation potential or 9.9 g CO 2 .L –1 PW brine) and for reproducible control of the produced calcium carbonate (CaCO 3 ) product. A full factorial design of experiments was implemented to study the effects of reaction temperature, pH, and gaseous CO 2 concentration on the mineralization and CO 2 capture rates as well as product crystalline structure and morphology. A maximum CO 2 capture rate of 0.315 ± 0.007 kg.L –1 .d –1 was achieved at 25°C and 25% CO 2 . CO 2 gas to liquid phase mass transport is believed to be the rate limiting step. With improved reactor design and optimization, the proposed semi‐continuous mineralization process shows promise for scaling to a pilot scale CO 2 capture technology.

Bennett, Quinn [Institute for Sustainable Energy &↗

DOE OSTI2025

Conjugate Heat Transfer Modeling of Salt-Filled Fuel Pins for Stable Salt Reactor Safety Analysis

The Stable Salt Reactor (SSR) combines the proven structural design of light water reactor fuel assemblies with the inherent safety and fuel-cycle advantages of molten salt technology. In its fast reactor configuration, the SSR utilizes recycled nuclear waste as fuel, sealed within narrow salt-filled fuel pins and cooled by a surrounding liquid salt coolant. Reliable transfer of heat from the molten fuel salt through the cladding to the external coolant is essential for both reactor safety and performance. This work investigates conjugate heat transfer (CHT) in the SSR’s salt-filled fuel pins using NekRS, a high-fidelity spectral element computational fluid dynamics (CFD) solver. The analyses capture internal natural convection within the molten fuel salt and external forced convection in the coolant, under steady-state and transient operating conditions. Parametric studies evaluate how variations in reactor power and coolant flow rate influence heat transfer distributions and system response. The high-fidelity CFD results are time-averaged and post-processed for direct comparison with moderate-fidelity Reynolds-averaged Navier–Stokes (RANS) models, and for the development of reduced-order models within the SAM system code. These validated models support fast-running safety analyses of normal and off-normal transients, improving predictive capability for key safety margins. By integrating advanced CFD with system-level safety tools, this study strengthens the modeling framework for SSR design, reduces uncertainty in molten salt CHT simulations, and accelerates the engineering and licensing of next-generation nuclear reactors.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

DOE OSTI2020

Multiple-objective Reinforcement Learning for Inverse Design and Identification

The aim of inverse chemical design is to develop new molecules with given optimized molecular properties or objectives. Recently, generative deep learning (DL) networks are considered as the state-of-the-art in inverse chemical design and have achieved early success in generating molecular structures with desired properties in the pharmaceutical and material chemistry fields. However, satisfying a large number (> 10 objectives) of molecular objectives is a limitation of current generative models. To improve the model’s ability to handle a large number of molecule design objectives, we developed a Reinforcement Learning (RL) based generative framework to optimize chemical molecule generation. Our use of Curriculum Learning (CL) to fine-tune the pre-trained generative network allowed the model to satisfy up to 21 objectives and increase the generative network’s robustness. The experiments show that the proposed multiple-objective RL-based generative model can correctly identify unknown molecules with an 83% to 100% success rate, compared to the baseline approach of 0%. Additionally, this proposed generative model is not limited to just chemistry research challenges; we anticipate that problems that utilize RL with multiple objectives will benefit from this framework.

reinforcement learning, generative model, inverse ↗

DOE OSTI2022

Effect of bacterial cell addition on Fe(III) reduction and soil organic matter transformation in a farmland soil

The coupled biogeochemical processes of Fe(III) reduction and organic matter transformation profoundly impact terrestrial carbon cycling. However, little is known about the microbial role in soil organic matter (SOM) transformation during Fe(III) bio-reduction. Here we investigated the bio-reduction behavior of a black farmland soil and corresponding SOM transformation under circumneutral and anoxic conditions. A model dissimilatory Fe reducing bacterium, Geobacter sulfurreducens, was added in either live or dead form in order to enhance Fe(III) reduction in soil and to evaluate the accompanying transformation of SOM. The progress of Fe reduction was monitored and SOM transformation was characterized by various spectroscopy methods. Results showed that addition of either dead or live G. sulfurreducens cells increased the Fe(III) reduction rate and extent. Without cell addition, SOM transformation was insignificant within 13 days of incubation, only with some consumption of aliphatic/protein compounds, apparently due to their higher bio-degradability. Addition of dead or live cells resulted in more drastic SOM transformation, but through different mechanisms. With dead cell amendment, cell necromass and debris stimulated the activity of indigenous soil microbes by serving as extra carbon/energy sources. During Fe(III) reduction, the aliphatic/protein compounds were preferentially consumed by indigenous microbial communities, similar to the treatment without cell addition but with a greater extent of consumption. In comparison, addition of live G. sulfurreducens cells stimulated degradation of less bioavailable compounds, including more saturated and higher molecular weight SOM. It is possible that fast depletion of labile SOM by live G. sulfurreducens cells favored utilization of less bioavailable molecules (such as those with more aromatic structures) by the originally dormant species in native microbial community, suggesting an active role of live Fe(III)-reducing bacteria in affecting SOM transformation. In addition, fast assimilation of microbial related carbon, such as aromatic proteins and microbial byproducts, into SOM pools was also observed. Overall, our results suggest that addition of Fe(III)-reducing bacteria to a native soil can enhance Fe(III) reduction and accelerate the turnover of SOM through various mechanisms. The study provides new insights into coupled Fe(III) reduction and SOM transformation, as well as the “priming effect” of SOM using microbial cells as substrate.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2023

The Effect of the SEI Layer Mechanical Deformation on the Passivity of a Si Anode in Organic Carbonate Electrolytes

The solid electrolyte interphase (SEI) on a Si negative electrode in carbonate-based organic electrolytes shows intrinsically poor passivating behavior, giving rise to unsatisfactory calendar life of Li-ion batteries. Moreover, mechanical strains induced in the SEI due to large volume changes of Si during charge-discharge cycling could contribute to its mechanical instability and poor passivating behavior. This study elucidates the influence that static mechanical deformation of the SEI has on the rate of unwanted parasitic reactions at the Si/electrolyte interface as a function of electrode potential. Further, the experimental approach involves the utilization of Si thin-film electrodes on substrates with disparate elastic moduli, which either permit or suppress the SEI deformation in response to Si volume changes upon charging-discharging. We find that static mechanical stretching and deformation of the SEI results in an increased parasitic electrolyte reduction current on Si. Furthermore, attenuated total reflection and near-field Fourier-transform infrared nanospectroscopy reveal that the static mechanical stretching and deformation of the SEI fosters a selective transport of linear carbonate solvent through, and nanoconfinement within, the SEI. These, in turn, promote selective solvent reduction and continuous electrolyte decomposition on Si electrodes, reducing the calendar life of Si anode-based Li-ion batteries. Finally, possible correlations between the structure and chemical composition of the SEI layer and its mechanical and chemical resilience under prolonged mechanical deformation are discussed in detail.

25 ENERGY STORAGE↗

DOE OSTI2020

Demand response for variable renewable energy integration: A proposed approach and its impacts

Not Available

McPherson, Madeleine↗

DOE OSTI2023

Ultrafast Switching of Interfacial Thermal Conductance

Dynamical control of thermal transport at the nanoscale provides a time-domain strategy for optimizing thermal management in nanoelectronics, magnetic devices, and thermoelectric devices. However, the rate of change available for thermal switches and regulators is limited to millisecond time scales, calling for a faster modulation speed. Here, in this work, time-resolved X-ray diffraction measurements and thermal transport modeling reveal an ultrafast modulation of the interfacial thermal conductance of an FeRh/MgO heterostructure as a result of a structural phase transition driven by optical excitation. Within 90 ps after optical excitation, the interfacial thermal conductance is reduced by a factor of 5 and lasts for a few nanoseconds, in comparison to the value at the equilibrium FeRh/MgO interface. The experimental results combined with thermal transport calculations suggest that the reduced interfacial thermal conductance results from enhanced phonon scattering at the interface where the lattice experiences transient in-plane biaxial stress due to the structural phase transition of FeRh. Our results suggest that optically driven phase transitions can be utilized for ultrafast nanoscale thermal switches for device application.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA NTRSDate not supplied

Fluid & Thermal Analysis of a Manifold Microchannel Heat Sink

A three-dimensional (3-D) numerical model has been developed to study the fluid flow and heat transfer through a manifold-microchannel (MMC) heat sink, a microfluidic cooling system designed as a heat dissipation solution for compact, high-powered electronic systems. An MMC consists of a 3-D manifold structure that distributes working fluid through alternating inlet and outlet manifold channels that guide the fluid to and from the microchannels, shortening the flow length and thereby, reducing the pressure drop across the system. Wide bandgap semiconductors such as silicon carbide (SiC) are increasingly utilized due to their ability to enable smaller electronic devices and components to operate more efficiently at higher frequencies. These semiconductors can greatly benefit from the MMC, which can extract all the heat produced by compact, high-powered electronics, enabling them to achieve optimal performance. The MMC also utilizes an embedded cooling approach which allows for fabrication directly within SiC-based electronics, resulting in significant mass and weight savings and lower thermal resistance than conventional heat sink designs. This paper outlines the methods used to conduct fluid and thermal analysis of different MMC configurations for flow parameters such as flow rate and inlet flow conditions. This study involves both steady state and transient thermal analysis as a gradually increasing heat flux is applied to the system over time, which is representative of the heat dissipation from the electronics over a given period. Results from the analysis show that the MMC is capable of effectively dissipating heat flux of ~100 W/cm2 while maintaining considerably low pressure drop (< 1 kPa) and thermal resistance (< 1 K/W) for certain single-phase working fluids.

manifold microchannel↗

NASA NTRSDate not supplied

Fluid & Thermal Analysis of a Manifold Microchannel Heat Sink

manifold microchannel↗

NASA NTRS2002

Demonstrating Acquisition of Real-Time Thermal Data Over Fires Utilizing UAVs

A disaster mitigation demonstration, designed to integrate remote-piloted aerial platforms, a thermal infrared imaging payload, over-the-horizon (OTH) data telemetry and advanced image geo-rectification technologies was initiated in 2001. Project FiRE incorporates the use of a remotely piloted Uninhabited Aerial Vehicle (UAV), thermal imagery, and over-the-horizon satellite data telemetry to provide geo-corrected data over a controlled burn, to a fire management community in near real-time. The experiment demonstrated the use of a thermal multi-spectral scanner, integrated on a large payload capacity UAV, distributing data over-the-horizon via satellite communication telemetry equipment, and precision geo-rectification of the resultant data on the ground for data distribution to the Internet. The use of the UAV allowed remote-piloted flight (thereby reducing the potential for loss of human life during hazardous missions), and the ability to "finger and stare" over the fire for extended periods of time (beyond the capabilities of human-pilot endurance). Improved bit-rate capacity telemetry capabilities increased the amount, structure, and information content of the image data relayed to the ground. The integration of precision navigation instrumentation allowed improved accuracies in geo-rectification of the resultant imagery, easing data ingestion and overlay in a GIS framework. We focus on these technological advances and demonstrate how these emerging technologies can be readily integrated to support disaster mitigation and monitoring strategies regionally and nationally.

Ambrosia, Vincent G.↗

DOE OSTI2023

Lifetime and Degradation Study of Poly(Methyl Methacrylate) via a Data-Driven Study Protocol Approach

We report to optimize and extend the service life of polymeric materials in outdoor environments, a domain knowledge-based and data-driven approach was utilized to quantitatively investigate the temporal evolution of degradation modes, mechanisms, and rates under various stepwise accelerated exposure conditions. Six formulations of poly(methyl methacrylate) (PMMA) with different combinations of stabilizing additives, including one unstabilized formulation, were exposed in three accelerated weathering conditions. Degradation was dependent on wavelength as samples in UV light at 340 nm (UVA) exposure showed the most yellowing. The unstabilized PMMA formulation showed much higher yellowness index values (59.5) than stabilized PMMA formulations (2–12). Urbach edge analysis shows a shift toward longer wavelength from 285 to 500 nm with increasing exposure time and an increased absorbance around 400 nm of visible region as the unstabilized samples increase in yellowing. The degradation mechanisms of PMMA were tracked using induced absorbance to dose at specific wavelengths that correspond to known degradation mechanisms. The degradation pathway of PMMA was modeled in a framework using network structural equation modeling (netSEM). netSEM showed changes in degradation pathway as PMMA transition stages of degradation.

36 MATERIALS SCIENCE↗

DOE OSTI2024

Isomer-resolved unimolecular dynamics of the hydroperoxyalkyl intermediate (•QOOH) in cyclohexane oxidation

The oxidation of cycloalkanes is important in the combustion of transportation fuels and in atmospheric secondary organic aerosol formation. A transient carbon-centered radical intermediate (•QOOH) in the oxidation of cyclohexane is identified through its infrared fingerprint and time- and energy-resolved unimolecular dissociation dynamics to hydroxyl (OH) radical and bicyclic ether products. Although the cyclohexyl ring structure leads to three nearly degenerate •QOOH isomers (β-, γ-, and δ-QOOH), their transition state (TS) barriers to OH products are predicted to differ considerably. Selective characterization of the β-QOOH isomer is achieved at excitation energies associated with the lowest TS barrier, resulting in rapid unimolecular decay to OH products that are detected. A benchmarking approach is employed for the calculation of high-accuracy stationary point energies, in particular TS barriers, for cyclohexane oxidation (C 6 H 11 O 2 ), building on higher-level reference calculations for the smaller ethane oxidation (C 2 H 5 O 2 ) system. The isomer-specific characterization of β-QOOH is validated by comparison of experimental OH product appearance rates with computed statistical microcanonical rates, including significant heavy-atom tunneling, at energies in the vicinity of the TS barrier. Master-equation modeling is utilized to extend the results to thermal unimolecular decay rate constants at temperatures and pressures relevant to cyclohexane combustion.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗