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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 469 records · Page 26
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Effects of temperature and time on supercritical methanol Co-Liquefaction of rice straw and linear low-density polyethylene wastes

We report that biofuels are particularly attractive and play an increasingly important role in sustainable energy. However, biofuels originating from lignocellulosic biomass (LCB) are extremely challenging because of their low carbon content, low stability, and high oxygen content. This work evaluates the supercritical methanol (scMeOH) co-liquefaction of rice straw and linear low-density polyethylene (LLDPE) at temperature range of 240-340 °C for 0-2 h, to obtain hydrocarbons (HCs)-rich oil and carbon-rich solid product. Results show that reaction temperature dominated the yield and properties of products, but not the holding time. Among parameters tested, 30.07 wt% oil yield with 75.79% HCs content and 33.05 wt% oil yield with 70.91% HCs content were obtained at 300 °C for 1 h and 1.5 h, respectively. Simultaneously, the remaining solid products were still as high as 53.85 wt% with a carbon content of 79.59% and 48.28 wt% with carbon content of 81.34% under 300 °C for 1 h and 1.5 h, respectively. Ultimate analysis, FT-IR, TGA, and SEM show that solid products could be used as sustainable carbon resources, and solid fuel rather than soil amendment because of risk of micro plastic or adsorbent due to smooth surface without pores.

09 BIOMASS FUELS↗
DOE OSTI2025

Measurement of spin-density matrix elements in 𝜙⁡(1020) → 𝐾$^{0}_{𝑆}$⁢𝐾$^{0}_{𝐿}$ photoproduction with a linearly polarized photon beam at 𝐸 𝛾 = 8.2–8.8 GeV

We measure the spin-density matrix elements (SDMEs) for the photoproduction of 𝜙⁡(1020) off of the proton in its decay to 𝐾$^{0}_{𝑆}$⁢𝐾$^{0}_{𝐿}$, using 105 pb −1 of data collected with a linearly polarized photon beam using the GlueX experiment. The SDMEs are measured in nine bins of the squared four-momentum transfer 𝑡 in the range −𝑡=0.15−1.0 GeV 2 , providing the first measurement of their 𝑡 dependence for photon beam energies of 𝐸 𝛾 = 8.2−8.8 GeV. We confirm the dominance of Pomeron exchange in this region and put constraints on the contribution of other Regge exchanges. We also find that helicity amplitudes where the helicity of the photon and 𝜙⁡(1020) differ by two units are negligible.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2023

Analysis of neptunium oxides produced through modified direct denitration

Production of neptunium-237 ( 237 Np) target materials for plutonium-238 ( 238 Pu) radioisotope thermoelectric generators (RTGs) for deep space exploration requires advanced chemistry and engineering development. Currently, the domestic Pu-238 Supply Program at Oak Ridge National Laboratory produces neptunium dioxide (NpO 2 ) for target material using a modified direct denitration (MDD) flowsheet. Although the chemistry, reaction mechanisms, and product characteristics of MDD are well understood for uranium, corresponding studies of the neptunium system are still needed to continue optimization of target material properties, production equipment design, and production flowsheets. Here, the objective of this work is to characterize crystalline phases, morphology, surface texture, and particle size of NpO 2 produced via MDD reactions. Solid-phase characterization techniques, including powder X-ray diffraction (pXRD) and scanning electron microscopy with energy-dispersive spectroscopy (SEM-EDS), were employed to achieve this objective. Subsequent data processing using the Morphological Analysis for Material Attribution (MAMA) software was performed to analyze particle morphology and size. Broadly, the powders were found to contain a mixture of NpO 2 and Np 2 O 5 after denitration with a variety of morphologies. After high-firing, the product was found to be NpO 2 with a typical polycrystalline oxide morphology and a grain size ranging from 0.72 to 0.94 µm. These analyses provide knowledge on the reaction pathway for a non-traditional NpO 2 synthesis method and offer additional unique insight into production-scale environments for transuranic materials.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2021

Gas-phase pyrolysis of trans 3-pentenenitrile: competition between direct and isomerization-mediated dissociation

The flash pyrolysis of trans 3-pentenenitrile (3-PN, CH 3 –$CH=CH$–CH 2 –CN) was studied by combining the results of VUV photoionization mass spectra with broadband microwave spectra recorded as a function of the temperature of the pyrolysis tube. The two separated functional groups (vinyl and nitrile) open up isomerization as an initial step in competition with unimolecular dissociation. Primary products were detected by keeping the 3-PN concentration low and limiting reaction times to the traversal time of the gas in the pyrolysis tube (~100 μs). The reaction is quenched and products are cooled by expansion into vacuum before interrogation over the 8–18 GHz region using chirped-pulse broadband methods. 118 nm VUV photoionization of the same reaction mixture provides a means of detecting all products with ionization potentials below 10.5 eV with minimal fragmentation. These results are combined with a detailed computational investigation of the C 5 H 7 N and related potential energy surfaces, leading to a consistent picture of the unimolecular decomposition of 3-PN. Loss of two H-atoms to form a 79 amu product is proven from its microwave transitions to contain trans-Z-2,4-pentadienenitrile, while no pyridine is observed. Methyl loss, HCN loss, and breaking the central C(2)–C(3) bond all occur following isomerization of the position of the double bond, thereby opening up low-energy pathways to these decomposition channels.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Understanding the effect of organic coatings on 4-nitrostyrene hydrogenation selectivity over Pt/TiO 2 catalysts

The hydrogenation of 4-nitrostyrene was investigated over Pt/TiO 2 catalysts to understand the effects of different catalyst coatings on product selectivity and reaction rates. This reaction is a much-investigated selectivity probe due to difficulty in controlling reactivity between the nitro and vinyl groups of 4-nitrostyrene, with C=C reduction generally being more favorable. 4-Nitrostyrene hydrogenation reactions were carried out in a batch reactor using uncoated, organothiol coated, phosphonic acid (PA) coated, and ion-conducting polymer (ionomer) coated catalysts. Thiols form dense coatings on Pt surfaces, whereas PAs preferentially accumulate on TiO 2 ; ionomer binding preference is unknown for this type of catalyst. The coating densities of the thiols and PAs were varied to observe the effects of loading on catalytic activity and reaction selectivity relative to the uncoated catalyst. Changes in selectivity were observed for catalysts with all coatings, with thiol coatings shifting selectivity towards the nitro reduction product, 4-vinylaniline (4-VA), and both ionomer and PA coatings shifting towards 4-ethylnitrobenzene, the olefin hydrogenation product. It was observed that selectivity toward 4-VA increased with thiol coating density, where 1,2-benzenedithiol (BDT) coated catalysts exhibited a selectivity of >99%. These changes were attributed to the identity of the adsorption sites blocked by the different coatings: blocking of metal sites via thiols decreased the rate of C=C hydrogenation, whereas blocking of TiO 2 sites by PAs decreased the rate of nitro group hydrogenation. The changes observed for ionomer and PA coatings suggested that ionomers, like PAs, bind preferentially to the metal oxide support rather than the active metal. This work provides new support to the proposal that nitro group hydrogenation preferentially occurs on TiO 2 sites after hydrogen spillover and underscores how selection of ligand functionality can be used to tune catalyst selectivity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Plastic waste gasification for low-carbon hydrogen production: a comprehensive review

Hydrogen is one of the most important feedstocks for the chemical industry, power production, and the decarbonization of other sectors that rely on natural gas. The production of hydrogen from plastics enables sustainable use of plastic waste and offers significant environmental benefits. Gasification emerges as a promising route for chemical recycling, converting plastic into hydrogen and other valuable chemicals. Although the gasification of plastic waste has recently gained attention, the number of studies regarding low-carbon hydrogen production is still limited. The effective integration of carbon capture, utilization, and storage (CCUS) is essential for achieving low-carbon hydrogen production via gasification, which enables the efficient capture and storage of CO 2 emissions. Incorporating coal waste and biomass into plastic gasification can synergistically enhance reforming reactions for hydrogen production, reduce tar content, and resolve feeding issues caused by plastic stickiness. Based on the previous studies, this paper briefly reviews the mechanisms of plastic gasification including plastic depolymerization, reforming, tar and char formation, and gasification; the discussions on feedstocks and effects of operating conditions on H 2 production including plastic-type, temperature, steam/carbon ratio, equivalence ratio, and catalysts; and the integration of CCUS and alternative recovery processes in plastic gasification for low-carbon hydrogen.

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

Assessment of the impact of reactor residence time distribution on non-equilibrium product selectivity of polypropylene pyrolysis using reactive molecular dynamics simulations

Mass residence time distribution (RTD) is considered to be an important factor controlling the product selectivity in the pyrolysis of biomass and plastic wastes along with the pyrolysis chemistry. However, due to the complex pyrolysis chemistry of biomass and plastic waste, the coupling between the reaction chemistry, RTD, and product selectivity is challenging to understand. Here, we introduce a reaction molecular dynamics-based method to examine pyrolysis chemistry and species timescales to assess the impact of RTD on product selectivity and yield. To validate this method, reactive molecular dynamics simulations were conducted for polypropylene pyrolysis and its non-equilibrium product selectivity using 6 different RTDs. We find that the RTD and the reaction chemistry control the peak non-equilibrium product concentrations. The peak monomer (C 3 H 6 ) concentration during pyrolysis can be increased by up to 25 % by using a narrow RTD in the case of polypropylene pyrolysis. We also find that product selectivity is strongly affected by the average residence time and RTD. This coupling between the reaction chemistry, RTD, and product selectivity highlights the need to understand detailed reaction chemistry to control RTD and optimize non-equilibrium product selectivity during polymer and biomass pyrolysis. The present method provides a new way to design RTD for reactors to reach maximized product selectivity of plastic waste and biomass.

33 ADVANCED PROPULSION SYSTEMS↗
DOE OSTI2020

Performance enhancement and degradation mechanism identification of a single-atom Co–N–C catalyst for proton exchange membrane fuel cells

Development of platinum group metal (PGM)-free catalysts for oxygen reduction reaction (ORR) has been a strategic research topic for proton exchange membrane (PEM) fuel cells. Present state-of-art PGM-free ORR catalysts are Fe, N co-doped carbon (Fe-N-C) catalysts, which unfortunately exhibit instability concerns. Herein, we report a stable atomically dispersed Co, N co-doped carbon (Co-N-C) catalyst with high Co content of 1.0 at% and the active site, i.e., the coordination of Co, is CoN2+2 in nature. The Co-N-C catalyst demonstrated high ORR activity comparable to, and high stability over 3 times better than, that of the Fe-N-C catalyst. It also achieved a high activity of 22 mA cm2 at 0.9 ViR-free and a power density of 0.61 W cm-2 under 1.0 bar H2/O2. Further, we identify two main degradation mechanisms of the PGM-free catalysts: catalyst oxidation by H2O2/radicals and demetalation. The improved stability of Co-N-C relative to Fe-N-C is attributed to less Fenton-reactive nature of Co and significantly enhanced resistance to demetalation of Co-N-C.

Xie, Xiaohong↗
DOE OSTI2020

Carbon Nanotube Formation on Cr-Doped Ferrite Catalyst during Water Gas Shift Membrane Reaction: Mechanistic Implications and Extended Studies on Dry Gas Conversions

A nanocrystalline chromium-doped ferrite (FeCr) catalyst was shown to coproduce H2 and multiwalled carbon nanotubes (MWCNTs) during water gas shift (WGS) reaction in a H2-permselective zeolite membrane reactor (MR) at reaction pressures of ~20 bar. The FeCr catalyst was further demonstrated in the synthesis of highly crystalline and dimensionally uniform MWCNTs from a dry gas mixture of CO and CH4, which were the apparent sources for MWCNT growth in the WGS MR. In both the WGS MR and dry gas reactions, the operating temperature was 500 °C, which is significantly lower than those commonly used in MWCNT production by chemical vapor deposition (CVD) method from CO, CH4, or any other precursor gases. Extensive ex situ characterizations of the reaction products revealed that the FeCr catalyst remained in partially reduced states of Fe3+/Fe2+ and Cr6+/Cr3+ in WGS membrane reaction while further reduction of Fe2+ to Fe0 occurred in the CO/CH4 dry gas environments. The formation of the metallic Fe nanoparticles or catalyst surface dramatically improved the crystallinity and dimensional uniformity of the MWCNTs from dry gas reaction as compared to that from WGS reaction in the MR. Reaction of the CO/CH4 mixture containing 500 ppmv H2S also resulted in high-quality MWCNTs similar to those from the H2S-free feed gas, demonstrating excellent sulfur tolerance of the FeCr catalyst that is practically meaningful for utilization of biogas and cheap coal-derived syngas.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Indirect measurement of the 90 Sr ⁢(𝑛, 𝛾)⁢ 91 Sr reaction cross section and the implications for astrophysical Zr production

Here, the intermediate neutron-capture process (𝑖 process) has gained notable traction within the past decade as a way to describe stellar abundance observations which cannot be explained by the slow and rapid neutron-capture processes. Despite the general success of 𝑖-process models, many open questions remain. Among the observations, Zr stands out, as its elemental abundance is difficult to replicate with available 𝑖-process models, while the reactions that affect its production through the 𝑖 process are close enough to stability to study experimentally. Here, we present the experimental constraint of the nuclear level density and 𝛾-strength function (𝛾 SF) of 91 Sr using the 𝛽-Oslo method, which were then input into the TALYS Hauser-Feshbach code to produce the first experimental constraint of the 90 Sr ⁢(𝑛, 𝛾)⁢ 91 Sr capture reaction. This constraint was used alongside that of 92 Sr ⁢(𝑛, 𝛾)⁢ 93 Sr for a reduction in the uncertainty of [Y/Zr] production in the 𝑖-process relevant environmental neutron density of 10 13.5 and 10 14.5 neutrons/cm 3 .

Physics - Nuclear physics and radiation physics↗
DOE OSTI2026

Synthesis and Properties of Bulk Mg 3 WN 4 in a Wurtzite-Derived Structure

Experimental synthesis of theoretically predicted materials with controlled elemental coordination environments can lead to the realization of useful properties, such as facile ion transport or ferroelectric switching. Among such materials are ternary nitrides in the Mg−W−N composition space, where several stable and metastable compounds have been predicted and synthesized recently in bulk and film forms. Here, we report for the first time on the bulk synthesis of Mg 3 WN 4 in a wurtzite-derived crystal structure via a solid-state metathesis reaction. In situ synchrotron powder X-ray diffraction shows how the ion exchange proceeds from Li 6 WN 4 + MgCl 2 precursors to Mg 3 WN 4 + LiCl products, with the reaction starting slowly near 380 °C and completing by 600 °C, including the presence of a competing disordered rocksalt-derived phase (Mg,W)N above 440 °C. The follow-up ex situ powder synthesis at 400 °C for 0.5 h with 10% excess MgCl 2 reveals the cation-ordered nature of the wurtzite-derived Mg 3 WN 4 structure with polar symmetry confirmed by second-harmonic generation measurements. Optical absorption spectra, chemical composition analysis, and electron microscopy imaging suggest that bulk Mg 3 WN 4 obtained via metathesis reaction is prone to defect formation. Overall, this study shows that selective ex situ synthesis of the phase-pure ternary nitrides, informed by in situ measurements, is possible by carefully controlling the thermal budget of the reaction and paves the way toward property characterization of the Mg 3 WN 4 wurtzite-derived material.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Selective Recovery of Critical Minerals from Simulated Electronic Wastes Via Reaction‐Diffusion Coupling

Abstract Atom‐ and energy‐efficient chemical separations are urgently needed to meet the surging demand for critical materials that has strained supply chains and threatened environmental damage. In this study, we used reaction‐diffusion coupling to separate iron, neodymium, and dysprosium ions from model feedstocks of permanent magnets, which are typically found in electronic wastes. Feedstock solutions were placed in contact with a hydrogel loaded with potassium hydroxide and/or dibutyl phosphate, resulting in complex precipitation patterns as the various metal ions diffused into the reaction medium. Specifically, we observed the precipitation of up to 40 mM of iron from the feedstock, followed by the enrichment of 73 % dysprosium, and the extraction of >95 % neodymium product at a further distance from the solution‐gel interface. We designed a series of experiments and simulations to determine the relevant ion diffusivities, D Nd =5.4×10 −10 and D Dy =5.1×10 −10 m 2 /s, and precipitation rates, k Nd =1.0×10 −5 and k Dy =5.0×10 −3 m 9 mol −3 s −1 , which enabled a numerical model to be established for predicting the distribution of products in the reaction medium. Our proof‐of‐concept study validates reaction‐diffusion coupling as an effective and versatile approach for critical materials separations, without relying on ligands, membranes, resins, or other specialty chemicals.

Wang, Qingpu [Physical and Computational Sciences ↗
DOE OSTI2023

Pynta-An Automated Workflow for Calculation of Surface and Gas-Surface Kinetics

Many important industrial processes rely on heterogeneous catalytic systems. However, given all possible catalysts and conditions of interest, it is impractical to optimize most systems experimentally. Automatically generated microkinetic models can be used to efficiently consider many catalysts and conditions. However, these microkinetic models require accurate estimation of many thermochemical and kinetic parameters. Manually calculating these parameters is tedious and error prone, involving many interconnected computations. Here, we present Pynta, a workflow software for automating the calculation of surface and gas–surface reactions. Pynta takes the reactants, products, and atom maps for the reactions of interest, generates sets of initial guesses for all species and saddle points, runs all optimizations, frequency, and IRC calculations, and computes the associated thermochemistry and rate coefficients. It is able to consider all unique adsorption configurations for both adsorbates and saddle points, allowing it to handle high index surfaces and bidentate species. Pynta implements a new saddle point guess generation method called harmonically forced saddle point searching (HFSP). HFSP defines harmonic potentials based on the optimized adsorbate geometries and which bonds are breaking and forming that allow initial placements to be optimized using the GFN1-xTB semiempirical method to create reliable saddle point guesses. This method is reaction class agnostic and fast, allowing Pynta to consider all possible adsorbate site placements efficiently. We demonstrate Pynta on 11 diverse reactions involving monodenate, bidentate, and gas-phase species, many distinct reaction classes, and both a low and a high index facet of Cu. Our results suggest that it is very important to consider reactions between adsorbates adsorbed in all unique configurations for interadsorbate group transfers and reactions on high index surfaces.

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

On the Rate Constant for NH 2 +HO 2 and Third-Body Collision Efficiencies for NH 2 +H(+M) and NH 2 +NH 2 (+M)

In low-temperature flash photolysis of NH 3 /O 2 /N 2 mixtures, the NH 2 consumption rate and the product distribution is controlled by the reactions NH 2 + HO 2 → products (R1), NH 2 + H (+M) → NH 3 (+M) (R2), and NH 2 + NH 2 (+M) → N 2 H 4 (+M) (R3). In the present work, published flash photolysis experiments by, among others, Cheskis and co-workers, are re-interpreted using recent direct measurements of NH 2 + H (+N 2 ) and NH 2 + NH 2 (+N 2 ) from Altinay and Macdonald. To facilitate analysis of the FP data, relative third-body collision efficiencies compared to N 2 for R2 and R3 were calculated for O 2 and NH 3 as well as for other selected molecules. We report results were in good agreement with the limited experimental data. Based on reported NH 2 decay rates in flash photolysis of NH 3 /O 2 /N 2 , a rate constant for NH 2 + HO 2 → NH 3 + O 2 (R1a) of $k_{1\text{a}}$ = 1.5(±0.5) × 10 14 cm 3 mol –1 s –1 at 295 K was derived. This value is higher than earlier determinations based on the FP results but in good agreement with recent theoretical work. Kinetic modeling of reported N 2 O yields indicates that NH 2 + HO 2 → H 2 NO + O (R1c) is competing with R1a, but perturbation experiments with addition of CH4 indicate that it is not a dominating channel. Measured HNO profiles indicate that this component is formed directly by NH 2 + HO 2 → HNO + H 2 O (R1b), but theoretical work indicates that R1b is only a minor channel. Based on this analysis, we estimate $k_{1\text{c}}$ = 2.5 × 10 13 cm 3 mol –1 s –1 and $k_{1\text{b}}$ = 2.5 × 10 12 cm 3 mol –1 s –1 at 295 K, with significant uncertainty margins.

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

Tandem Electrocatalytic–Thermocatalytic Conversion of CO 2 to Aromatic Hydrocarbons

The reaction of CO 2 with H 2 O to produce aromatic hydrocarbons (benzene, toluene, ethylbenzene, and xylene isomers) (BTEX) represents a promising pathway for converting CO 2 to value-added liquid products. However, this reaction cannot be achieved in a single electrochemical or thermochemical process. This work utilizes tandem electrochemical-thermochemical reactors as a new paradigm by starting with CO 2 and H 2 O as the feed in a membrane electrode assembly (MEA) to produce C 2 H 4 , which subsequently undergoes thermochemical aromatization using a Gallium- and Phosphorus-modified zeolite ZSM-5 catalyst (Ga/ZSM-5/P) at ambient pressure to produce BTEX. The current study also demonstrates the potential advantage of the tandem strategy in mitigating negative effects of water by testing the tandem reactor system under different hydration conditions and by performing in-situ X-ray diffraction (XRD) and X-ray absorption (XAS) characterization of the aromatization catalysts. Finally, these results highlight the advantage of using the tandem process with the use of a water trap before the thermochemical reactor.

10 SYNTHETIC FUELS↗
DOE OSTI2020

Microkinetic simulation and fitting of the temperature programmed reaction of methanol on CeO 2 (111): H 2 and H 2 O + V production

The kinetics and mechanism for temperature programmed reaction following adsorption of an adsorbate can be better understood by simulation and fitting with comparison to experiment. A case study is presented here for the chemistry of adsorption of methanol on a CeO 2 (111) surface followed by heating. The gas products observed are CH 3 OH, CH 2 O, H 2 , H 2 O, CO, CO 2 . At low temperatures (< 500 K), there is formation of H 2 and H 2 O, where the H 2 O formation is accompanied by lattice oxygen vacancy (V) formation and is thus important in determining the selectivity towards different products. Microkinetic modeling was performed using a recently published method for fitting to gain mechanistic knowledge of the H 2 and H 2 O + V formation at < 500 K. In the kinetic models used here, most of the H 2 and H 2 O + V V formation can be explained by a mechanism in which a metastable state of hydrogen on the surface (H*) acts as an intermediate. Two possibilities were investigated for the source of the metastable H* intermediate: H* from CH bond breaking of methoxies, or promotion of H+ to H* via electron transfer from ionic methoxies absorbed in oxygen vacancies (CH 3 O - /V). From this study, we consider the latter to be more likely at < 500 K. For the H 2 O formation, it was found to be critical that H 2 O cannot dissociate directly on oxygen vacancies. Finally, catalytic chemistry was observed in simulations, including catalytic formation of oxygen vacancies. Various features of the experimental results were reproduced, including methoxies being the major carbon containing species on the surface at < 500 K.

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↗