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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 73 records · Page 4
All sourcesNASA NTRSDOE OSTI
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 OSTI2020

Nonequilibrium Solvent Effects during Photodissociation in Liquids: Dynamical Energy Surfaces, Caging and Chemical Identity

In the gas phase, potential energy surfaces can be used to provide insight into the details of photochemical reaction dynamics. In solution, however, it is unclear what potential energy surfaces, if any, can be used to describe even simple chemical reactions such as the photodissociation of a diatomic solute. In this paper, we use mixed quantum/classical (MQC) molecular dynamics (MD) to study the photodissociation of $Na$ $^+_2$ in both liquid Ar and liquid tetrahydrofuran (THF). We examine both the gas-phase potential surfaces and potentials of mean force (PMF), which assume that the solvent remains at equilibrium with the solute throughout the photodissociation process and show that neither resemble a nonequilibrium dynamical energy surface that is generated by taking the time integral of work. For the photodissociation of $Na$ $^+_2$ in liquid Ar, the dynamical energy surface shows clear signatures of solvent caging, and the degree of caging is directly related to the mass of the solvent atoms. For $Na$ $^+_2$ in liquid THF, local specific interactions between the solute and solvent lead to changes in chemical identity that create a kinetic trap that effectively prevents the molecule from dissociating. Here, the results show that nonequilibrium effects play an important role even in simple solution-phase reactions, requiring the use of dynamical energy surface to understand such chemical events.

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

Surface‐Enforced Alignment of Reprogrammable Liquid Crystalline Elastomers

Abstract Liquid crystalline elastomers (LCEs) are stimuli‐responsive materials capable of undergoing large deformations. The thermomechanical response of LCEs is attributable to the coupling of polymer network properties and disruption of order between liquid crystalline mesogens. Complex deformations have been realized in LCEs by either programming the nematic director via surface‐enforced alignment or localized mechanical deformation in materials incorporating dynamic covalent chemistries. Here, the preparation of LCEs via thiol‐Michael addition reaction is reported that are amenable to surface‐enforced alignment. Afforded by the thiol‐Michael addition reaction, dynamic covalent bonds are uniquely incorporated in chemistries subject to surface‐enforce alignment. Accordingly, LCEs prepared with complex director profiles are able to be programmed and reprogrammed by (re)activating the dynamic covalent chemistry to realize distinctive shape transformations.

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

Interplay of intercalation dynamics and lithium plating in monolithic and architectured graphite anodes during fast charging

Fast charging of high-capacity anodes is challenging due to lithium plating reactions, which lead to poor cycling performance and safety concerns. Thus, accurate predictions of plating onset and an understanding of this electrochemical process are crucial for robust battery design. However, the most commonly used models, based on porous electrode theory (e.g., the pseudo-2D model), are notoriously difficult to calibrate due to their complexity, limiting their predictive power. This work studies the process of lithium plating during fast charging of (small-particle) graphite half-cells by measuring local reaction progression and plating behavior using optical operando techniques. These experiments employ a realistic 1D graphite electrode geometry with commercially-relevant mass loading charged at fast charge rates. It is demonstrated that the local reaction progression and plating onset can not only be predicted accurately with a p2D numerical model, but that these processes follow a simple scaling law. Remarkably, the entire reaction histories of different electrodes charged at different rates (e.g., 160 μm thickness at 0.5C, 111 μm at 1C or 66 μm at 4C) were observed to have self-similar intercalation profiles. It is demonstrated that plating onset is in turn governed by the reaction profile which explains why both processes exhibit the same scaling behavior. Finally, operando measurements of local reaction dynamics are conducted for the first time in electrodes with channeled architectures, quantitatively determining how channels affect reaction uniformity and plating onset. Together, these results reveal underlying simplicity in the complex electrochemical environment of fast charging and lithium plating, improving understanding of this process. These fundamental insights are broadly applicable for design processes, modeling and experimental evaluation of lithium ion batteries.

25 ENERGY STORAGE↗
DOE OSTI2026

Measurements of the inert Hugoniot and observation of mechanical ignition in Ni(V) + Al reactive multilayers via x-ray diffraction

This study investigates the inert Hugoniot response, mechanical ignition, and reaction dynamics of Ni(V)+Al multilayers during longitudinal, laser-driven shock compression experiments. Ni(V)+Al multilayers, known for their self-propagating exothermic reactions, were subjected to longitudinal stresses exceeding 50 GPa using the laser shock facility within the Dynamic Compression Sector (DCS) at the Advanced Photon Source (APS). In situ x-ray diffraction (XRD) revealed that Ni(V) and Al were not in equilibrium during compression, with stress discrepancies attributed to twinning, grain structure effects, and/or dislocation density. However, the measured inert Hugoniot closely matched prior experimental and computational studies, confirming the utility of XRD for measuring the equation of state of thin, complex materials. Additionally, reaction was observed at significantly higher stresses than reported previously using laser-launched flyers. This discrepancy suggests a strong influence of externally imposed shear stress on reaction thresholds, which likely arose from deviations in flyer planarity during past experiments. Full reaction of the multilayer occurred within 40 ns after shock-wave passage, evidenced by complete melting of the constituents. Eulerian hydrocode simulations replicated experimental conditions, providing insights into equilibrium dynamics and experimental artifacts. The results highlight how even small shear forces facilitate ignition in Ni(V)+Al multilayers at lower stresses.

Crystallography↗
DOE OSTI2026

Cation Data for the East River Watershed, Colorado (2014-2025)

This data package contains mean values for cation concentration for water samples taken from the East River Watershed in Colorado. Inductively coupled plasma mass spectrometry (ICP-MS) has been used to measure the concentrations of elements of interest simultaneously for the East River Watershed, Colorado groundwater and surface water samples to inform insights on the biogeochemistry processes within the watershed. The East River is part of the Watershed Function Scientific Focus Area (WFSFA) located in the Upper Colorado River Basin, United States. For samples collected prior to 06-16-2021, the instrumentation, Elan DRC II, PerkinElmer SCIEX, automatically switches among the three models necessary to analyze all 37 elements. These 37 elements include: (1) Lithium (Li), Beryllium (Be), Boron (B), Sodium (Na), Magnesium (Mg), Aluminium (Al), Silicon (Si), Phosphorus (P), Titanium (Ti), Cobalt (Co), Nickel (Ni), Copper (Cu), Zinc (Zn), Germanium (Ge), Arsenic (As), Rubidium (Rb), Strontium (Sr), Zirconium (Zr), Molybdenum (Mo), Silver (Ag), Cadmium (Cd), Tin (Sn), Antimony (Sb), Caesium (Cs), Barium (Ba), Europium (Eu), Lead (Pb), Thorium (Th), Uranium (U) using standard model, argon Ar as reaction gas, (2) Potassium (K), Calcium (Ca), Vanadium (V), Chromium (Cr), Manganese (Mn), Iron (Fe) using dynamic reaction cell (DRC) model, ammonia NH3 as reaction gas, and (3) Phosphorus (P) and Selenium (Se) using DRC model, oxygen O2 as reaction gas. Note for the samples with higher concentrations of chloride (Cl-), asenic (As) concentrations were analysed with DRC model (oxygen O2 as reaction gas) to avoid the interference of chloride. For samples collected on and after 06-16-2021, an advanced Agilent 8900 triple quadrupole inductively coupled plasma mass spectrometry system (Agilent 8900 QQQ ICP-MS, Agilent Technologies) has been used to measure the concentrations of interested 36 elements simultaneously for environmental samples, including (1) Lithium (Li), Beryllium (Be) and Boron (B) using standard no gas mode, (2) Sodium (Na), Magnesium (Mg), Aluminium (Al) Phosphorus (P), Potassium (K), Chromium (Cr), Manganese (Mn), Iron (Fe), Cobalt (Co), Nickel (Ni), Copper (Cu), Zinc (Zn), Germanium (Ge), Arsenic (As), Rubidium (Rb), Strontium (Sr), Zirconium (Zr), Molybdenum (Mo), Silver (Ag), Cadmium (Cd), Tin (Sn), Antimony (Sb), Cesium (Cs), Barium (Ba), Europium (Eu), Lead (Pb), Thorium (Th) and Uranium (U) using standard helium (He) collision mode, (3) Titanium (Ti) and Vanadium (V) using high Energy (HEHe) helium (He) collision mode, and (4) Silicon (Si), Calcium (Ca) and Selenium (Se) using standard H2 reaction mode. All samples were prepared/diluted with 2% (v/v) ultrapure nitric acid in Milli-Q water (18.2 mega ohm-cm), and analyzed under a rigorous quality assurance and quality control (QA/QC) process. This data package contains (1) a zip file (cation_data_2014_2025.zip) containing a total of 5,849 files: 5.848 data files of cation data from across the Lawrence Berkeley National Laboratory (LBNL) Watershed Function Scientific Focus Area (SFA) which is reported in .csv files per location and a locations.csv (1 file) with latitude and longitude for each location; (2) a file-level metadata (v6_20260901_flmd.csv) file that lists each file contained in the dataset with associated metadata; (3) a data dictionary (v6_20260901_dd.csv) file that contains terms/column_headers used throughout the files along with a definition, units, and data type; (4) PDF and docx files for the detemination of Method Detection Limits (MDLs) for ICP-MS PerkinElmer DRC II instrumentation (Detemination_of_Method_Detection_Limits__MDLs__for_ICP_MS__PerkinElmer_Elan_DRC_II__LBL_Bldg74_Lab214D) for samples before November 2021; (5) PDF and docx files for the determination of MDLs for ICP-MS Agilent 8900 QQQ instrumentation (ICP_MS_Analysis_detection_limits_and_QA_QC_WenmingDong_updated_2026-08-06) for samples November 2021 and onward. Missing values within the anion data files are noted as either "-9999" or "0.0" for not detectable (N.D.) data. There are a total of 113 locations containing cation data. Update on 2021-04-11: Added Detemination of Method Detection Limits (MDLs) for ICP-MS document, which can be accessed as a PDF or with Microsoft Word. Update on 2022-06-10: versioned updates to this dataset was made along with these changes: (1) updated cation data for all locations up to 2021-12-31, (2) removal of units from column headers in datafiles, (3) added row underneath headers to contain units of variables, (4) removed suffix and prefix on two variables (“aqberylliumion_asberyllium” and “aqlithiumion_aslithium”), (5) added -9999 for empty numerical cells, and (6) the addition of the file-level metadata (flmd.csv) and data dictionary (dd.csv) were added to comply with the File-Level Metadata Reporting Format. Update on 2022-09-09: Updates were made to reporting format specific files (file-level metadata and data dictionary) to correct swapped file names, add additional details on metadata descriptions on both files, add a header_row column to enable parsing, and add version number and date to file names (v2_20220909_flmd.csv and v2_20220909_dd.csv). Update on 2023-08-08: Updates were made to both the data files and reporting format specific files. New available anion data was added, up until 2023-01-05. The file level metadata and data dictionary files were updated to reflect the additional data added. Update on 2024-03-11: Updates were made to both the data files and reporting format specific files. New available anion data was added, up until 2023-10-16. Further, revisions to the data files were made to remove incorrect data points (from 1970 and 2001). The reporting format specific files were updated to reflect the additional data added. Updated versions of the PDF and docx files for determination of MDLs for ICP-MS data were added to this dataset for samples starting in November 2021. Update on 2025-05-15: Updates were made to both the data files and reporting format specific files. New available cation data was added, up until the end of WY2024 (September 30, 2024). International Generic Sample Numbers (IGSNs), when registered, were added to the data files. The reporting format specific files were updated to reflect the additional data added. Update on 2026-09-01: Updates were made to both the data files and reporting format specific files. New available cation data was added, up until the end of WY2025 (September 30, 2025). Updated versions, as of 2026-08-06, of the PDF and docx files for determination of MDLs for ICP-MS data were added to this dataset for samples starting in November 2021.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2021

Updated systematics of intermediate-energy single-nucleon removal cross sections

The body of experimental measurements of intermediate-energy reactions that remove a single nucleon from a secondary beam of neutron- or proton-rich nuclei continues to grow. These data have been analyzed consistently using an approximate, eikonal-model treatment of the reaction dynamics combined with appropriate shell-model descriptions of the projectile initial state, the bound final states spectrum of the reaction residue, and single-particle removal strengths computed from their wave-function overlaps. Here, the systematics of the ratio R s of the measured inclusive cross section to all bound final states and the calculated cross section to bound shell-model states—in different regions of the nuclear chart and involving both very weakly bound and strongly bound valence nucleons—is important in relating the empirically deduced orbital occupancies to those from the best available shell-model predictions. Importantly, several new higher-energy measurements, for which the sudden-approximation aspect of the dynamical description is placed on an even stronger footing, now supplement the previously analyzed measurements. These additional data sets are discussed. Their R s values are shown to conform to and reinforce the earlier-observed systematics, with no indication that the approximately linear reduction in R s with increasing nucleon separation energy is a consequence of a breakdown of the sudden approximation.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2022

Ultrafast electron diffraction: Visualizing dynamic states of matter

Since the discovery of electron-wave duality, electron scattering instrumentation has developed into a powerful array of techniques for revealing the atomic structure of matter. Beyond detecting local lattice variations in equilibrium structures with the highest possible spatial resolution, recent research efforts have been directed toward the long-sought-after dream of visualizing the dynamic evolution of matter in real time. The atomic behavior at ultrafast timescales carries critical information on phase transition and chemical reaction dynamics, the coupling of electronic and nuclear degrees of freedom in materials and molecules, and the correlation among structure, function, and previously hidden metastable or nonequilibrium states of matter. Ultrafast electron pulses play an essential role in this scientific endeavor, and their generation has been facilitated by rapid technical advances in both ultrafast laser and particle accelerator technologies. Here this review presents a summary of the noteworthy developments in this field in the last few decades. The physics and technology of ultrafast electron beams is presented with an emphasis on the figures of merit most relevant for ultrafast electron diffraction experiments. Recent developments in the generation, manipulation, and characterization of ultrashort electron beams aimed at improving the combined spatiotemporal resolution of these measurements are discussed. The fundamentals of electron scattering from atomic matter and the theoretical frameworks for retrieving dynamic structural information from solid-state and gas-phase samples is described. Essential experimental techniques and several landmark works that have applied these approaches are also highlighted to demonstrate the widening applicability of these methods. Ultrafast electron probes with ever-improving capabilities, combined with other complementary photon-based or spectroscopic approaches, hold tremendous potential for revolutionizing our ability to observe and understand energy and matter at atomic scales.

43 PARTICLE ACCELERATORS↗
DOE OSTI2021

Single Atom Catalysts: A Review of Characterization Methods

Abstract Single atom catalysts (SACs) harbor a potential to exceed nanoparticle catalysts in terms of activity, stability and selectivity in a growing number of chemical reactions. Although their investigation is attracting significant attention, important fundamental questions focusing on key physicochemical properties of SACs (e. g., structure – property relationships, structural dynamics, reaction‐driven restructuring) remain unanswered. A main challenge for research in the field is how to reliably characterize the environments of single atoms in the presence of complicating factors such as low weight loadings, strong metal‐support interactions, and atomic and multiscale heterogeneity of bonding in the single atom sites. This review addresses this challenge – identifying catalytically relevant features of physicochemical properties of single atoms (charge state, electronic structure, atomic configuration, bonding interactions with a support) and surveying advanced tools/methods for characterizing them. The review places a strong emphasis on multimodal methods exploiting X‐ray absorption, emission and photoelectron spectroscopies, and provides several examples from the authors’ research that demonstrate their use as powerful tools for SAC characterization.

Kottwitz, Matthew↗
DOE OSTI2023

Evidence of Zintl Intermediate Phase and Its Impacts on Li and Na Storage Performance of Pb-Based Alloying Anodes

Anode materials based on conversion and alloying reactions are promising to achieve high energy density of advanced sodium-ion batteries (SIBs). While the chemical similarities between sodium and lithium as alkali elements make the benchmarking strategy practical in developing new high-performance anodes, simply borrowing the anode material from one system to the other does not always guarantee success unless it is based on sound understanding of both Li- and Na-reaction mechanisms. In this work, we report the Na storage performance of a Pb-based anode and its fundamental reaction dynamics. In contrast to its excellent electrochemical performances in Li cells (reversible ~600 mAh/g), the newly developed Pb@PbO–C nanocomposite anode has limited electrochemical Na reaction properties showing moderate capacity and rate performances (~300 mAh/g at 20 mA/g). Synchrotron-based X-ray diffraction and absorption spectroscopy studies reveal the fundamental differences in the Na and Li reaction mechanism of the Pb-based anode. Further, unlike Li reaction, the unique Na reaction mechanism involves the formation of a highly ionic NaPb Zintl phase, which comprises tetrahedral Pb 4 clusters, as an intermediate phase. The strong covalent character of the Pb 4 Zintl clusters adversely affects the electronic conductivity and thus limits the electrochemical performance of the Pb-based anode in Na cells. These findings provide new insights applicable to developing high-performance alloying anode materials.

25 ENERGY STORAGE↗
DOE OSTI2026

Neutron skins probed in proton knockout from neutron-rich nuclei

Proton-induced quasifree knockout reactions provide a powerful probe of nuclear single-particle structure and reaction dynamics in both stable and neutron-rich nuclei. Here, in this work, we develop a unified theoretical framework for the calculation of inclusive (𝑝, 2⁢𝑝) and sequential (𝑝, 3⁢𝑝) reaction cross sections and fragment momentum distributions at intermediate and relativistic energies. The approach is based on a probabilistic extension of Glauber multiple-scattering theory combined with microscopic nuclear densities obtained from Hartree-Fock-Bogoliubov calculations using Skyrme energy-density functionals. We focus in particular on the sensitivity of total cross sections and longitudinal momentum dispersions to neutron-skin thickness along isotopic chains. Our results indicate that both (𝑝, 2⁢𝑝) and (𝑝, 3⁢𝑝) reactions exhibit a systematic decrease of cross section and momentum width with increasing neutron excess, reflecting enhanced attenuation and surface bias induced by neutron skins. The effect is significantly stronger for two-proton removal, suggesting that (𝑝, 3⁢𝑝) reactions may offer enhanced sensitivity to isovector nuclear structure. These findings establish proton-induced knockout reactions as complementary hadronic probes of neutron skins and the density dependence of the nuclear symmetry energy.

direct reactions↗
DOE OSTI2022

Bayesian optimization of dynamic Ce( III ) electrooxidation

Abstract Cerium(III/IV) is a redox couple with promising applications in redox flow batteries and redox‐mediated water electrolyzers, but due to its high oxidation potential, parasitic oxygen evolution can occur and decrease the Faradaic efficiency (FE) of the oxidation reaction. Dynamic potential dosing can help balance the transport limitations and the electrooxidation rates, allowing for control over the cerium(III) concentration near the electrode, enhancing FE. Due to the large number of possible pulsing operating conditions, Bayesian optimization (BO) was used to rapidly identify the optimal potential pulses. With an active pulse voltage of 2.5 V vs. Ag/AgCl, the maximum FE achieved was 0.91 (active pulse time = 5 ms, resting pulse time = 136 ms), underscoring the need for long inactive times for cerium(III) diffusion to the electrode. Furthermore, a multiobjective BO was performed to identify optimal trade‐offs between FE and the partial current density to achieve improvements over constant current operation.

Engineering↗
DOE OSTI2021

Revealing the etching process of water-soluble Au 25 nanoclusters at the molecular level

Etching (often considered as decomposition) is one of the key considerations in the synthesis, storage, and application of metal nanoparticles. However, the underlying chemistry of their etching process still remains elusive. Here, we use real-time electrospray ionization mass spectrometry to study the reaction dynamics and size/structure evolution of all the stable intermediates during the etching of water-soluble thiolate-protected gold nanoclusters (Au NCs), which reveal an unusual “recombination” process in the oxidative reaction environment after the initial decomposition process. Interestingly, the sizes of NC species grow larger and their ligand-to-metal ratios become higher during this recombination process, which are distinctly different from that observed in the reductive growth of Au NCs (e.g., lower ligand-to-metal ratios with increasing sizes). The etching chemistry revealed in this study provides molecular-level understandings on how metal nanoparticles transform under the oxidative reaction environment, providing efficient synthetic strategies for new NC species through the etching reactions.

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

Prediction of photodynamics of 200 nm excited cyclobutanone with linear response electronic structure and ab initio multiple spawning

Simulations of photochemical reaction dynamics have been a challenge to the theoretical chemistry community for some time. In an effort to determine the predictive character of current approaches, we predict the results of an upcoming ultrafast diffraction experiment on the photodynamics of cyclobutanone after excitation to the lowest lying Rydberg state (S 2 ). A picosecond of nonadiabatic dynamics is described with ab initio multiple spawning. Herein we use both time dependent density functional theory (TDDFT) and equation-of-motion coupled cluster singles and doubles (EOM-CCSD) theory for the underlying electronic structure theory. We find that the lifetime of the S 2 state is more than a picosecond (with both TDDFT and EOM-CCSD). The predicted ultrafast electron diffraction spectrum exhibits numerous structural features, but weak time dependence over the course of the simulations.

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

One Collision—Two Substituents: Gas–Phase Preparation of Xylenes under Single–Collision Conditions

The fundamental reaction pathways to the simplest dialkylsubstituted aromatics—xylenes (C 6 H 4 (CH 3 ) 2 )—in high-temperature combustion flames and in low-temperature extraterrestrial environments are still unknown, but critical to understand the chemistry and molecular mass growth processes in these extreme environments. Exploiting crossed molecular beam experiments augmented by state-of-the-art electronic structure and statistical calculations, this study uncovers a previously elusive, facile gas-phase synthesis of xylenes through an isomer-selective reaction of 1-propynyl (methylethynyl, CH 3 CC) with 2-methyl-1,3-butadiene (isoprene, C 5 H 8 ). The reaction dynamics are driven by a barrierless addition of the radical to the diene moiety of 2-methyl-1,3-butadiene followed by extensive isomerization (hydrogen shifts, cyclization) prior to unimolecular decomposition accompanied by aromatization via atomic hydrogen loss. This overall exoergic reaction affords a preparation of xylenes not only in high-temperature environments such as in combustion flames and around circumstellar envelopes of carbon-rich Asymptotic Giant Branch (AGB) stars, but also in low-temperature cold molecular clouds (10 K) and in hydrocarbon-rich atmospheres of planets and their moons such as Triton and Titan. Furthermore, our study established a hitherto unknown gas-phase route to xylenes and potentially more complex, disubstituted benzenes via a single collision event highlighting the significance of an alkyl-substituted ethynyl-mediated preparation of aromatic molecules in our Universe.

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

One Collision—Two Substituents: Gas–Phase Preparation of Xylenes under Single–Collision Conditions

The fundamental reaction pathways to the simplest dialkylsubstituted aromatics—xylenes (C 6 H 4 (CH 3 ) 2 )—in high-temperature combustion flames and in low-temperature extraterrestrial environments are still unknown, but critical to understand the chemistry and molecular mass growth processes in these extreme environments. Exploiting crossed molecular beam experiments augmented by state-of-the-art electronic structure and statistical calculations, this study uncovers a previously elusive, facile gas-phase synthesis of xylenes through an isomer-selective reaction of 1-propynyl (methylethynyl, CH 3 CC) with 2-methyl-1,3-butadiene (isoprene, C 5 H 8 ). The reaction dynamics are driven by a barrierless addition of the radical to the diene moiety of 2-methyl-1,3-butadiene followed by extensive isomerization (hydrogen shifts, cyclization) prior to unimolecular decomposition accompanied by aromatization via atomic hydrogen loss. This overall exoergic reaction affords a preparation of xylenes not only in high-temperature environments such as in combustion flames and around circumstellar envelopes of carbon-rich Asymptotic Giant Branch (AGB) stars, but also in low-temperature cold molecular clouds (10 K) and in hydrocarbon-rich atmospheres of planets and their moons such as Triton and Titan. Furthermore, our study established a hitherto unknown gas-phase route to xylenes and potentially more complex, disubstituted benzenes via a single collision event highlighting the significance of an alkyl-substituted ethynyl-mediated preparation of aromatic molecules in our Universe.

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

Photo-excitation of long-lived transient intermediates in ultracold reactions

In many chemical reactions, the transformation from reactants to products is mediated by transient intermediate complexes. For gas-phase reactions involving molecules with a few atoms, these complexes typically live on the order of 10 ps or less before dissociating, and are therefore rarely influenced by external processes. Here, we demonstrate that the transient intermediate complex K 2 Rb 2 *, formed from collisions between ultracold KRb molecules, undergoes rapid photo-excitation in the presence of a continuous-wave laser source at 1,064 nm, a wavelength commonly used to confine ultracold molecules. These excitations are facilitated by the exceptionally long lifetime of the complex under ultracold conditions. Indeed, by monitoring the change in the complex population after the sudden removal of the excitation light, we directly measure the lifetime of the complex to be 360 ± 30 ns, in agreement with our calculations based on the Rice–Ramsperger–Kassel–Marcus (RRKM) statistical theory. Furthermore, our results shed light on the origin of the two-body loss widely observed in ultracold molecule experiments. Additionally, the long complex lifetime, coupled with the observed photo-excitation pathway, opens up the possibility to spectroscopically probe the structure of the complex with high resolution, thus elucidating the reaction dynamics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗