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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 289 records · Page 16
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

The Effect of Physically Based Ice Radiative Processes on Greenland Ice Sheet Albedo and Surface Mass Balance in E3SM

Abstract A significant portion of surface melt on the Greenland Ice Sheet (GrIS) is due to dark ice regions in the ablation zone, where solar absorption is influenced by the physical properties of the ice, light absorbing constituents (LACs), and the overlying crustal surface or melt ponds. Earth system models (ESMs) typically prescribe the albedo of ice surfaces as a constant value in the visible and near‐infrared spectral regions. This work advances ESM ice radiative transfer modeling by (a) incorporating a physically based radiative transfer model (SNow, ICe and Aerosol Radiation model Adding‐Doubling Version 4; SNICAR‐ADv4) into the Energy Exascale Earth System Model (E3SM), (b) determining spatially and temporally varying bare ice physical properties over the GrIS ablation zone from satellite observations to inform SNICAR‐ADv4, and (c) assessing the impacts on simulated GrIS albedo and surface mass balance associated with modeling of more realistic bare ice albedo. GrIS‐wide bare ice albedo in E3SMv2 is overestimated by ∼4% in the visible and ∼7% in the near‐infrared wavelengths compared to the Moderate Resolution Imaging Spectroradiometer. Our bare ice physical property retrieval method found that LACs, ice crustal surfaces, and melt ponds reduce visible albedo by 30% in the bare ice region of the GrIS ablation zone. The realistic bare ice albedo reduces surface mass balance by ∼145 Gt, or 0.4 mm of sea‐level equivalent between 2000 and 2021 compared to the default E3SM. This work highlights the importance of simulating bare ice albedo accurately and realistically to improve our ability to quantify changes in the GrIS surface mass and radiative energy budgets.

58 GEOSCIENCES↗
DOE OSTI2020

Raytracing

The raytracing (spectrally specific radiative transfer that does not couple back to the hydrodynamic evolution) code was developed because it helps improve our understanding of the physics of explosive events, validates computational physics codes, and estimates optical signals that are cheaper and safer than experiments involving high explosives. The raytracing code can also produce simulations that are useful to analyze what we can understand with sensors, such as determining what we can discriminate with sensors, like the presence of certain metals or the amount of soot. In addition, simulations can provide extra validations to computational physics to help us better understand discrepancies.

45 MILITARY TECHNOLOGY, WEAPONRY, AND NATIONAL DEF↗
DOE OSTI2021

Seasonal Cycle of Idealized Polar Clouds: Large Eddy Simulations Driven by a GCM

The uncertainty in polar cloud feedbacks calls for process understanding of the cloud response to climate warming. As an initial step toward improved process understanding, we investigate the seasonal cycle of polar clouds in the current climate by adopting a novel modeling framework using large eddy simulations (LES), which explicitly resolve cloud dynamics. Resolved horizontal and vertical advection of heat and moisture from an idealized GCM are prescribed as forcing in the LES. The LES are also forced with prescribed sea ice thickness, but surface temperature, atmospheric temperature, and moisture evolve freely without nudging. A semigray radiative transfer scheme without water vapor and cloud feedbacks allows the GCM and LES to achieve closed energy budgets more easily than would be possible with more complex schemes. This enables the mean states in the two models to be consistently compared, without the added complications from interaction with more comprehensive radiation. Furthermore, we show that the LES closely follow the GCM seasonal cycle, and the seasonal cycle of low-level clouds in the LES resembles observations: maximum cloud liquid occurs in late summer and early autumn, and winter clouds are dominated by ice in the upper troposphere. Large-scale advection of moisture provides the main source of water vapor for the liquid-containing clouds in summer, while a temperature advection peak in winter makes the atmosphere relatively dry and reduces cloud condensate. The framework we develop and employ can be used broadly for studying cloud processes and the response of polar clouds to climate warming.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2026

Reduced instability growth and improved radiation trapping with optimized shock timing in double-shell inertial confinement fusion capsules

The double shell is a volume-burn inertial confinement fusion concept consisting of two concentric shells: a low-Z outer shell that collides with and transfers momentum to a high-Z inner shell which compresses and heats the thermonuclear fuel. The increased number of capsule interfaces and severe hydrodynamic instability of the high-density pusher during its acceleration phase provide challenges to the success of the double shell. Two-dimensional radiation-hydrodynamics simulations predict the hydrodynamic instability growth on the outer surface of the pusher can be greatly reduced through appropriate timing of two shocks that cross this interface. One of these shocks, unique to multi-shell designs, arises from radiation-driven ablation of the inner shell ahead of the main shock, the second shock of concern. The shock timing is optimized by increasing the thickness of a low-Z tamper layer exterior to the pusher, resulting in only minimal changes to the implosion timing. Reducing the instability growth on the outer surface of the high-Z pusher can dramatically decrease the modulations that feedthrough to the pusher inner surface, improving the efficacy of radiation trapping in the thermonuclear fuel and increasing the predicted thermonuclear yield by ≳20×.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2022

Implement and Test 3D Mortar Contact in BISON

We leverage the extension of the generation of mortar segment meshes to three dimensions in MOOSE’s framework to extend thermomechanical modeling capabilities to problems with three dimensions. A modular approach to gap heat transfer physics using the mortar finite element method was created and documented, mechanical contact was extended to three dimensions—including frictional behavior, performance and ease of use were improved, and steps towards scalability of solid mechanics problems involving contact were taken. Many of these new developments are demonstrated in the simulation of 3D light-water reactor (LWR) problems, where the thermomechanical interface problem is solved using the mortar finite element method. Usage of the mortar framework has improved convergence in 2D problems and has enabled employing friction in 3D problems, of which we show results of a short, local stack of 3D pellets. Consequently, the benefits of mortar in terms of solution convergence and quality are extended to three dimensions. Section 2 discusses fundamental developments that enabled the simulation of practical mortar problems in three dimensions and other general improvements, including the reduction of the derivative container size, the modification of dual basis computations when edge dropping (lack of secondary element projection) takes place, the improvement of conditioning when employing the VCP in-edge dropping conditions, and code usability and quality improvements. These latter code enhancements include the migration of tests using “old” mortar contact constraints to using dual mortar with a semi-smooth Newton solution strategy and the reuse of lower dimensional domains for straightforwardly setting up a mortar thermomechanical LWR problem, i.e. the MOOSE action is employed for mechanical contact and the thermal LWR action is employed to capture the gas conductance, contact, and radiation components of gap heat transfer physics. Independently of the mortar LWR thermal action, we developed a modular approach to gap heat transfer that resides in MOOSE and can be leveraged, e.g., in metallic fuel problems. This approach, whose code design based on MOOSE’s user objects to model specific physics was proposed by the maintenance activity, is detailed in Section 3. Based on the dual mortar finite element method, the frictional contact constraints were extended to three dimensions. A block sheared in two directions in and out of contact with a rigid plane is employed in Section 4 to show the way the approach handles changes in frictional states (e.g. stick to slip) within a competitive number of Newton iterations. Equations and numerical results on the use of the VCP with Cartesian Lagrange multipliers, whose combination enables their direct condensation, are described in Section 5.3. Two-dimensional and three-dimensional BISON LWR simulations are discussed in Section 6. Particularly, a stack of five eccentric pellets with a surface defect is simulated and the effect of pellet-cladding friction is assessed. Finally, conclusions are outlined in Section 7.

42 ENGINEERING↗
DOE OSTI2021

Pressurizer dynamic model and emulated programmable logic controllers for nuclear power plants cybersecurity investigations

This work demonstrates the functionality of the pressurizer using a fast-running three regions, non-equilibrium model and control programs of emulated PLCs. The state variables from an integrated model of primary loop in a representative PWR plant are communicated to the pressurizer’s emulated PLCs using a synchronized data transfer function. In turn, the PLCs communicate back instructions to the pressurizer model to adjust the pressure and water level to remain within preprogramed setpoints. Pressurizer model simultaneously solves the coupled mass and energy conservation equations in the saturated vapor and saturated and subcooled liquid regions using fixed step solver. Results demonstrate the response of the pressurizer model linked to an emulated pressure and water level PLCs in a simulated transient involving surge-in and surge-out events. The 50 ms response delay time for the emulated PLC insignificantly affects operation and predictions of the pressurizer model.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2022

Thermal radiation analysis of a pressurized oxy-coal combustor with discrete ordinate model

Concerns over climate change have led to numerous efforts in developing low-carbon energy technologies. Pressurized oxy-combustion (POC) is a promising candidate to reduce carbon emissions in power generation. Pressure strongly impacts thermal radiation, leading to a substantial difference in heat transfer between POC and conventional atmospheric pressure combustion. A good understanding of thermal radiation in POC is needed to aid new combustor development. The present work is a step in this direction, initiating a systematic analysis of thermal radiation and heat transfer in a pilot-scale POC combustor, which has been developed at Washington University in St. Louis (WUSTL). In a POC process, pulverized coal is burned under elevated pressure and O2-CO2 environment. Few researchers have investigated the thermal radiation of pressurized oxy-combustion. This work adopted the discrete ordinate model to simulate the radiation of a 1-D cylinder with predetermined conditions (temperature, pressure, gas compositions) to predict the influence of radiative properties of flue gas on the radiation in the combustor.

Li, Lei↗
DOE OSTI2020

Chirality transfer and chiral turbulence in gauge theories

Chirality transfer between fermions and gauge fields plays a crucial role for understanding the dynamics of anomalous transport phenomena such as the Chiral Magnetic Effect. In this proceeding we present a first principles study of these processes based on classical-statistical real-time lattice simulations of strongly coupled QED (e 2 N f = 64). Furthermore, our simulations demonstrate that a chirality imbalance in the fermion sector triggers chiral plasma instabilities in the gaugefield sector, which ultimately lead to the generation of long range helical magnetic fields via an self-similar turbulent cascade of the magnetic helicity.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2020

Simulation as a sustainable trading zone: Aiming at intergenerational justice

The paper, drawing on the example of simulation codes used in nuclear physics and high-energy physics, seeks to call attention to the ethical implications of discontinuing support for simulation codes and the loss of knowledge embodied in them. Predicated on the concept of trading zones and actor network models, the paper addresses the problem of extinction of simulation codes and attempts to understand their evolution and development within those frameworks. We show that simulation codes of closed type develop to the level of creoles, becoming local languages and standards of scientific centers and disappearing as their few main developers leave, whereas codes of open types become universal languages, imposing problemsolving patterns on the entire community and crowding out other codes. The paper suggests that because of simulations’ reliance on tacit knowledge, practices entrenched in codes cannot be exhaustively explicated or transmitted through writing alone; on the contrary, the life cycle of a simulation code is determined by the life cycle of its trading zone. We examine the extent to which both of these phenomena pose a risk to the preservation of knowledge. Bearing upon intergenerational ethics, we draw analogies between the pure intergenerational problem (PIP) and the problem of preserving the knowledge implemented in simulation codes and transmitting it to future generations. We argue that for the complete transfer of knowledge, it is necessary to develop and maintain inhabitability and sustainability of simulation trading zones in a controllable way, at least until the demand for these codes is warranted to cease in the future.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2022

SNICAR-ADv4: a physically based radiative transfer model to represent the spectral albedo of glacier ice

Abstract. Accurate modeling of cryospheric surface albedo is essential for our understanding of climate change as snow and ice surfaces regulate the global radiative budget and sea-level through their albedo and mass balance. Although significant progress has been made using physical principles to represent the dynamic albedo of snow, models of glacier ice albedo tend to be heavily parameterized and not explicitly connected with physical properties that govern albedo, such as the number and size of air bubbles, specific surface area (SSA), presence of abiotic and biotic light absorbing constituents (LACs), and characteristics of any overlying snow. Here, we introduce SNICAR-ADv4, an extension of the multi-layer two-stream delta-Eddington radiative transfer model with the adding–doubling solver that has been previously applied to represent snow and sea-ice spectral albedo. SNICAR-ADv4 treats spectrally resolved Fresnel reflectance and transmittance between overlying snow and higher-density glacier ice, scattering by air bubbles of varying sizes, and numerous types of LACs. SNICAR-ADv4 simulates a wide range of clean snow and ice broadband albedo (BBA), ranging from 0.88 for (30 µm) fine-grain snow to 0.03 for bare and bubble-free ice under direct light. Our results indicate that representing ice with a density of 650 kg m−3 as snow with no refractive Fresnel layer, as done previously, generally overestimates the BBA by an average of 0.058. However, because most naturally occurring ice surfaces are roughened “white ice”, we recommend modeling a thin snow layer over bare ice simulations. We find optimal agreement with measurements by representing cryospheric media with densities less than 650 kg m−3 as snow and larger-density media as bubbly ice with a Fresnel layer. SNICAR-ADv4 also simulates the non-linear albedo impacts from LACs with changing ice SSA, with peak impact per unit mass of LACs near SSAs of 0.1–0.01 m2 kg−1. For bare, bubble-free ice, LACs actually increase the albedo. SNICAR-ADv4 represents smooth transitions between snow, firn, and ice surfaces and accurately reproduces measured spectral albedos of a variety of glacier surfaces. This work paves the way for adapting SNICAR-ADv4 to be used in land ice model components of Earth system models.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2025

Sim2Real Autonomous Robotic Exploration [Poster]

Autonomous robots offer promising solutions for exploration in environments that are inaccessible or hazardous to humans. Despite this, physical training of such robots is often constrained by safety risks, high cost or limited accessibility. This project presents an end-to-end simulation to reality pipeline leveraging Nvidia Isaac Sim and Boston Dynamics' Spot to enable autonomous navigation in indoor environments. A reinforcement learning policy is first trained using Nvidia Isaac Lab to establish Spot's locomotion pattern. Virtual LiDAR sensors are then integrated to perform SLAM-based navigation using simulated odometry. Finally, the simulated navigation scheme is transferred to a physical Spot robot to inspect and record images of a real-world room by repeating the learnt trajectory. The proposed framework highlights the potential of scalable training in simulation and reliable deployment in physical environments. Future directions include dynamic trajectory generation in unseen and challenging environments and integration of environmental sensing like temperature, radiation or humidity via sensor and material simulation.

97 - MATHEMATICS AND COMPUTING↗
DOE OSTI2024

Automation and optimization of stopping and range of ions in matter simulation runtime

Prior to every ion implantation experiment a simulation of the ion range and other relevant parameters is performed using Monte-Carlo based codes. Although increasing computing power has improved the speed of these calculations, the demands on Monte-Carlo codes are also increasing, requiring evaluation of the optimal number of simulations while ensuring accuracy within threshold bounds. We evaluate the “Stopping and Range of Ions in Matter” (SRIM) code due to its widespread usage. We show how dividing simulations into multiple parallel simulations with different random seeds can lead to calculation speedup and find lower bounds for the required number of ion traces simulated based on an exemplar system of a Ga focused ion beam and a high energy C beam as used in high linear energy transfer testing. Here our results indicate simulations can yield results within the underlying data accuracy of SRIM at 10X and 100X shorter simulation time than the SRIM default values.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
DOE OSTI2026

Effect of soot concentration on radiative transport in a 2 m JP-8 pool fire

Hubbard et al. (2024) investigated conjugate heat transfer in a 7.9 m JP-8 pool fire, utilizing both heavily sooting and non-sooting fuel models. Their findings indicated that all models produced pool radiative heat fluxes within the measurement uncertainty for large-scale outdoor experiments. This study aims to further investigate the influence of soot concentration on radiative transport. To this end, Large Eddy Simulations (LES) of a 2 m diameter JP-8 pool fire were conducted, employing four turbulent combustion chemistry models: the Eddy Dissipation Concept (EDC) and three variants of flamelet model. Additionally, three variations of the one-equation subgrid scale turbulence kinetic energy model, and multiple mesh resolutions were utilized. The primary validation metrics were pool radiative heat flux and plume radiative fraction, with simulation data compared to experimental results published by Blanchat et al. (2010). The EDC model produced high soot concentrations near the pool surface, resulting in a significant shielding effect. In contrast, the flamelet combustion model has different kinetic limiters for soot production, leading to soot formation higher in the flame, where it can be more readily oxidized. Flamelet models incorporating both acetylene and benzene contributions to soot growth demonstrated better agreement with experimental data. To assess the sensitivity of pool radiative heat flux to soot mass concentration, we used a one-dimensional approximation over a wide range of soot concentrations and compared it to three-dimensional solutions obtained using Discrete Ordinates. Furthermore, this analysis illustrates the impacts of soot shielding and Turbulence Radiation Interactions (TRI), with TRI emission enhancement factors predicted to be in the range of 3–5 near the edges of the plume.

Computational fluid dynamics↗
DOE OSTI2026

Mesoscale Organization in Cumulus-Coupled Stratocumulus

Marine cloud systems cover a substantial portion of the world’s oceans. Most of these clouds form relatively close to the ocean surface, typically within one to two kilometers, a region referred to by meteorologists as the marine boundary layer. They are composed predominantly of liquid water, although ice particles can occur in mid- and high-latitude marine clouds during winter. In satellite imagery, these clouds appear bright against the darker ocean surface below, reflecting a large fraction of incoming sunlight back into space that would otherwise warm the ocean. Because marine boundary layer clouds cover such an extensive area of the ocean, they exert a significant influence on Earth’s overall transfer of solar energy absorbed by the surface and thermal energy emitted to space, a balance known as the planetary radiation budget. Marine boundary layer clouds are typically thin, and their formation and dissipation depend on a delicate balance between processes acting at the ocean surface below and the warm, dry air above. They are notoriously difficult to simulate accurately in weather forecast models, which often produce too few marine low clouds in midlatitudes and clouds in tropical regions that are excessively bright, meaning they reflect too much solar radiation. The marine boundary layer is frequently characterized by widespread overcast cloud cover that often transitions from a continuous, single-layer deck to more broken cloud fields toward the tropics. These transitions typically proceed through an intermediate stage in which shallow, broken clouds form beneath the overlying stratiform cloud deck. Once broken clouds develop below the overcast, they frequently self-organize into cloud clusters known as marine boundary layer convective complexes (MBLCCs), although the mechanisms governing the formation and organization of MBLCCs remain poorly understood. Accurately representing these transitions in long-range weather forecast models is essential because they influence the properties of air masses advected over the continental United States and Europe, and they become increasingly important for forecasts on seasonal and longer timescales. We employed two complementary approaches to investigate the processes controlling MBLCCs and their impact on marine cloud cover. Long-term observations from the U.S. Department of Energy’s Eastern North Atlantic (ENA) Observatory provided a unique dataset that allowed us to characterize fundamental properties of MBLCCs, including their typical size and frequency of occurrence. These observations were combined with high-resolution numerical simulations performed on supercomputers to examine the evolution of MBLCCs during cold-air outbreaks over the ENA region.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2024

Numerical investigation of mixing and heat transfer in a 7.9 m JP-8 pool fire

The response of objects engulfed in, and adjacent to, large-scale pool fires is of interest in accident and safety assessments. In this study, Fuego, a low-Mach turbulent reacting flow code was used to study conjugate heat transfer in a 7.9 m diameter JP-8 pool fire. Simulations were designed to replicate past experimental measurements (Blanchat et al., 2006) of incident heat flux to three cylindrical calorimeters in and around the pool fire. Two turbulent combustion models were compared directly - the eddy dissipation concept and a more recently developed unsteady flamelet model. First and second order spatial and temporal discretization schemes were also compared to assess the performance of low-dissipation numerical operators. Heat flux predictions to the transportation size calorimeter outside the fire were within experimental uncertainties. Inside the fire, experimental measurements were higher than predicted values and may have been a consequence of soot deposition and augmented participating media radiation from soot and fuel vapor. Simulation predictions improved in cases where turbulent kinetic energy and mixing were more resolved. This work, and others referenced herein, suggest that spatial resolution on the order of 0.5–1.0 cm may be required to fully resolve fluid instabilities, vortex production between fire plumes and crosswind, soot production, and fuel-air mixing. This presents a substantial computational challenge for safety assessments of engulfed objects in fully turbulent pool fires.

Conjugate heat transfer↗
DOE OSTI2024

Impact of mid- Z gas fill on dynamics and performance of shock-driven implosions at the OMEGA laser

Shock-driven implosions with 100% deuterium (D 2 ) gas fill compared to implosions with 50:50 nitrogen-deuterium (N 2 ⁢D 2 ) gas fill have been performed at the OMEGA laser facility to test the impact of the added mid-Ζ fill gas on implosion performance. Ion temperature (Τ ion ) as inferred from the width of measured DD-neutron spectra is seen to be 34%±6% higher for the N 2⁢ D 2 implosions than for the D 2 -only case, while the DD-neutron yield from the D 2 -only implosion is 7.2±0.5 times higher than from the N 2⁢ D 2 gas fill. The T ion enhancement for N 2 ⁢D 2 is observed in spite of the higher Z, which might be expected to lead to higher radiative loss, and higher shock strength for the D 2 -only versus N 2 ⁢D 2 implosions due to lower mass, and is understood in terms of increased shock heating of N compared to D, heat transfer from N to D prior to burn, and limited amount of ion-electron-equilibration-mediated additional radiative loss due to the added higher-Z material. Further, this picture is supported by interspecies equilibration timescales for these implosions, constrained by experimental observables. The one-dimensional (1D) kinetic Vlasov-Fokker-Planck code ifp and the radiation hydrodynamic simulation codes hyades (1D) and xrage [1D, two-dimensional (2D)] are brought to bear to understand the observed yield ratio. Comparing measurements and simulations, the yield loss in the N 2 ⁢D 2 implosions relative to the pure D 2 -fill implosion is determined to result from the reduced amount of D 2 in the fill (fourfold effect on yield) combined with a lower fraction of the D 2 fuel being hot enough to burn in the N 2 ⁢D 2 case. The experimental yield and T ion ratio observations are relatively well matched by the kinetic simulations, which suggest interspecies diffusion is responsible for the lower fraction of hot D 2 in the N 2 ⁢D 2 relative to the D 2 -only case. The simulated absolute yields are higher than measured; a comparison of 1D versus 2D XRAGE simulations suggest that this can be explained by dimensional effects. The hydrodynamic simulations suggest that radiative losses primarily impact the implosion edges, with ion-electron equilibration times being too long in the implosion cores. The observations of increased T ion and limited additional yield loss (on top of the fourfold expected from the difference in D content) for the N 2 ⁢D 2 versus D 2 -only fill suggest it is feasible to develop the platform for studying CNO-cycle-relevant nuclear reactions in a plasma environment.

47 OTHER INSTRUMENTATION↗
DOE OSTI2025

Ab Initio Molecular Dynamics Study of the Reduction of Acetone by the Hydrated Electron

We have investigated the reaction dynamics of the reduction of acetone by the solvated electron in water using ab initio molecular dynamics simulations at 298 and 373 K. The rate constants derived from the simulations are consistent with experimental observations that the reaction has a low activation energy. Detailed analyses carried out to shed light on the mechanism of the reaction show that solvent reorganization plays a key role as a reaction coordinate, as expected from the Marcus electron transfer theory. Furthermore, constrained density functional theory calculations indicate that the electronic coupling is large, placing the reaction in the adiabatic limit. Indeed, the activation energies and rate constants of the simulations are in accordance with the predictions of adiabatic Marcus theory.

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

Exploring the Unusual Reactivity of the Hydrated Electron with CO 2

Many questions remain about the reactions of the hydrated electron despite decades of study. Of particular note is the fact that they do not appear to follow the Marcus theory of electron transfer reactions, a feature that has yet to be explained. To investigate these issues, we use ab initio molecular dynamics (AIMD) simulations to investigate a one of the better studied reactions, the hydrated electron reduction of CO 2 . The rate constant for the hydrated electron-CO 2 reaction complex to react to form CO 2 - is, for the first time, estimated from AIMD simulations. Results at 298 and 373 K show the rate constant is insensitive to temperature, consistent with the low measured activation energy for the reaction, and the implications of this behavior are examined. The sampling provided by the simulations yields insight into the reaction mechanism. The reaction is found to involve both solvent reorganization and changes in the carbon dioxide structure. The latter lead to significant vibrational excitation of the bending and symmetric stretch vibrations in the CO 2 - product, indicating the reaction is vibrationally nonadiabatic. The former is estimated from calculation of an approximate collective solvent coordinate and the free energy in this coordinate is determined. Furthermore, these results indicate that AIMD simulations can reasonably estimate hydrated electron reaction activation energies and provide new insight into the mechanism that can help illuminate the features of this unusual chemistry.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗