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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 181 records · Page 10
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

The Surprising Dynamics of the McLafferty Rearrangement

We report femtosecond time-resolved measurements of the McLafferty rearrange- ment following the strong-field tunnel ionization of 2-pentanone, 4-methyl-2-pentanone, and 4,4- dimethyl-2-pentanone. The pump–probe-dependent yields of the McLafferty product ion are fit to a biexponential function with fast (~100 fs) and slow (~10 ps) time constants, the latter of which is faster for the latter two compounds. Following nearly instantaneous ionization, the fast time scale is associated with rotation of the molecule to a six-membered cyclic intermediate that facilitates transfer of the γ-hydrogen, while the ~50–100 times longer time scale is associated with a π-bond rearrangement and bond cleavage between the α- and β-carbons to produce the enol cation. Furthermore, these experimental measurements are supported by ab initio molecular dynamics trajectories, which further confirm the time scale of this important stepwise reaction in mass spectrometry.

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

SPARC-X: Quantum simulations at extreme scale - reactive dynamics from first principles

We have developed the massively parallel electronic structure code SPARC-X: a computational framework for performing Kohn-Sham Density Functional Theory (DFT) calculations that can scale linearly with the number of atoms in the system, while being able to leverage petascale and emerging exascale parallel computers to study chemical phenomena at unprecedented length and time scales. SPARC-X exploits a recent breakthrough in electronic structure methodologies: systematically improvable, strictly local, orthonormal, discontinuous real-space bases that efficiently and systematically capture the local chemistry of the system. With further adaptation using new machine-learning techniques and the use of the massively parallel Spectral Quadrature (SQ) electronic structure method, the algorithmic complexity and prefactor associated with DFT calculations involving semilocal as well as hybrid functionals are dramatically reduced. Using petascale computational resources, SPARC-X enables quantum mechanical simulations at length and time scales previously accessible only by empirical approaches, e.g., 1,000,000 atoms for a few picoseconds using semilocal functionals or 1,000 atoms for a few picoseconds using hybrid functionals. Using exascale resources, the sizes and times targeted are two orders of magnitude larger. Such a capability has applications in a wide variety of chemical sciences, including reactive interfaces where large length- and/or long time-scales are needed and traditional force fields fail. This is particularly important in dynamic catalysis, where bond breaking and formation must be understood in detail. We developed, tested, and employed the SPARC-X framework to understand the photocatalytic properties of TiO 2 nanoparticles, revealing finite size effects that cannot be captured with standard model systems or functionals. This integrated development and application strategy ensures that SPARC-X remains a robust, efficient, and scalable software package for quantum simulations on current petascale and emerging exascale computing resources.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2022

A multi-scale time-series dataset with benchmark for machine learning in decarbonized energy grids

The electric grid is a key enabling infrastructure for the ambitious transition towards carbon neutrality as we grapple with climate change. With deepening penetration of renewable resources, the reliable operation of the electric grid becomes increasingly challenging. In this paper, we present PSML, a first-of-its-kind open-access multi-scale time-series dataset, to aid in the development of data-driven machine learning (ML)-based approaches towards reliable operation of future electric grids. The dataset is synthesized from a joint transmission and distribution electric grid to capture the increasingly important interactions and uncertainties of the grid dynamics, containing power, voltage and current measurements over multiple spatio-temporal scales. Using PSML, we provide state-of-the-art ML benchmarks on three challenging use cases of critical importance to achieve: (i) early detection, accurate classification and localization of dynamic disturbances; (ii) robust hierarchical forecasting of load and renewable energy; and (iii) realistic synthetic generation of physical-law-constrained measurements. We envision that this dataset will provide use-inspired ML research in safety-critical systems, while simultaneously enabling ML researchers to contribute towards decarbonization of energy sectors.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2020

Deep convolutional neural networks for multi-scale time-series classification and application to disruption prediction in fusion devices

The multi-scale, mutli-physics nature of fusion plasmas makes predicting plasma events challenging. Recent advances in deep convolutional neural network architectures (CNN) utilizing dilated convolutions enable accurate predictions on sequences which have long-range, multi-scale characteristics, such as the time-series generated by diagnostic instruments observing fusion plasmas. Here we apply this neural network architecture to the popular problem of disruption prediction in fusion tokamaks, utilizing raw data from a single diagnostic, the Electron Cyclotron Emission imaging (ECEi) diagnostic from the DIII-D tokamak. ECEi measures a fundamental plasma quantity (electron temperature) with high temporal resolution over the entire plasma discharge, making it sensitive to a number of potential pre-disruptions markers with different temporal and spatial scales. Promising, initial disruption prediction results are obtained training a deep CNN with large receptive field ({$\sim$}30k), achieving an $F_1$-score of {$\sim$}91\% on individual time-slices using only the ECEi data.

convolutional neural networks↗
DOE OSTI2021

Mode-Selective Vibrational Energy Transfer Dynamics in 1,3,5-Trinitroperhydro-1,3,5-triazine (RDX) Thin Films

The coupling of inter- and intramolecular vibrations plays a critical role in initiating chemistry during the shock-to-detonation transition in energetic materials. In this work, we report on the subpicosecond to subnanosecond vibrational energy transfer (VET) dynamics of the solid energetic material 1,3,5-trinitroperhydro-1,3,5-triazine (RDX) by using broadband, ultrafast infrared transient absorption spectroscopy. Experiments reveal VET occurring on three distinct time scales: subpicosecond, 5 ps, and 200 ps. The ultrafast appearance of signal at all probed modes in the mid-infrared suggests strong anharmonic coupling of all vibrations in the solid, whereas the long-lived evolution demonstrates that VET is incomplete, and thus thermal equilibrium is not attained, even on the 100 ps time scale. Density functional theory and classical molecular dynamics simulations provide valuable insights into the experimental observations, revealing compression-insensitive time scales for the initial VET dynamics of high-frequency vibrations and drastically extended relaxation times for low-frequency phonon modes under lattice compression. Mode selectivity of the longest dynamics suggests coupling of the N–N and axial NO2 stretching modes with the long-lived, excited phonon bath.

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

Shallow-to-Deep Convective Transition in the Amazon (Final Report)

The frequent and extensive deep cloud formations over the Amazon Basin provide a vast area of atmospheric heating in the Tropics, forcing large-scale global circulations on daily to secular time scales. Motivated by the importance of these systems to the global climate system and the well-documented seasonal cycle in rainfall over the Amazon Basin, this study focused on improving understanding of the processes governing these systems on seasonal time scales and their impact on the typical growth of convection from early afternoon through evening, termed the shallow-to-deep transition. This study is based on observations from the Department of Energy (DOE) ARM Mobile Facility (AMF) near Manacapuru, Brazil collected during the Observations and Modeling of the Green Ocean Amazon (GOAmazon) field campaign from 1 January 2014 to 30 November 2015, together with total column water vapor (CWV) and surface meteorological observations from a dense Global Navigation Satellite System (GNSS) network within 50 km of the AMF site provided by the CHUVA Program collected in coordination with the GOAmazon campaign. The specific objectives of this study were to address the following questions: 1) What environmental conditions support the shallow-to-deep convective transition over the Central Amazon? 2) How does the relative importance of these conditions compare during the wet and dry seasons? 3) How are these conditions modulated by basin-scale transient forcing? 4) How well are these processes captured by regional model simulations convective resolving scale? Our main hypothesis was that intra-seasonal atmospheric disturbances were a primary driver of rainfall during the wet season in the Central Amazon, while localized surface heating of the land was the primary driver of enhanced rainfall during the dry season. Overall, our findings supported our hypothesis, with the convectively active phase of atmospheric Kelvin waves strongly favoring the development of larger, more organized rain systems during the wet season, while localized isolated deep convection dominated the types of rain events seen during the dry season. These results have implications for the predictability of rainfall over the Central Amazon and for its representation in climate and weather models.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2020

Electronic relaxation dynamics in [Au 25 (SR) 18 ] -1 (R = CH 3 , C 2 H 5 , C 3 H 7 , MPA, PET) thiolate-protected nanoclusters

Here we investigate the excited electron dynamics in [Au 25 (SR) 18 ] -1 (R = CH3, C 2 H 5 , C 3 H 7 , MPA, PET) [MPA = mercaptopropanoic acid, PET = phenylethylthiol] nanoparticles to understand how different ligands affect the excited state dynamics in this system. The population dynamics of the core and higher excited states lying in the energy range 0.00–2.20 eV are studied using a surface hopping method with decoherence correction in a real-time DFT approach. All of the ligated clusters follow a similar trend in decay for the core states (S 1 –S 6 ). The observed time constants are on the picosecond time scale (2–19 ps), which agrees with the experimental time scale, and this study confirms that the time constants observed experimentally could originate from core-to-core transitions and not from core-to-semiring transitions. In the presence of higher excited states, R = H, CH 3 , C 2 H 5 , C 3 H 7 , and PET demonstrate similar relaxations trends whereas R = MPA shows slightly different relaxation of the core states due to a smaller gap between the LUMO+1 and LUMO+2 gap in its electronic structure. The S 1 (HOMO → LUMO) state gives the slowest decay in all ligated clusters, while S 7 has a relatively long decay. Furthermore, separate electron and hole relaxations were performed on the [Au 25 (SCH 3 ) 18 ] -1 nanocluster to understand how independent electron and hole relaxations contribute to the overall relaxation dynamics.

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

Parallel expansion of a fuel pellet plasmoid

The problem of the assimilation of a cryogenic fuel pellet injected into a hot plasma is considered. Due to the transparency to ambient particles of the plasmoid, the localised region of high-density plasma created by ionisation of the ablated pellet material, electrons reach a ‘quasiequilibrium’ (QE) state which is characterised by a steady-state on the fastest collisional time scale. The simplified electron kinetic equation of the QE state is solved. Taking a velocity moment of the higher-order electron kinetic equation, which is valid on the expansion time scale, permits a fluid closure, yielding an evolution equation for the macroscopic parameters describing the QE distribution function. In contrast to the Braginskii equations, the closure does not require that electrons have a short mean free path compared with the size of density perturbations, and permits an anisotropic and highly non-Maxwellian distribution function. As the QE distribution function accounts for both trapped and passing electrons, the self-consistent electric potential that causes the expansion can be properly described, in contrast to earlier models of pellet plasmoid expansion with an unbounded potential. The plasmoid expansion is simulated using both a Vlasov model and a cold-fluid model for the ions. During the expansion plasmoid ions and electrons obtain nearly equal amounts of energy; as hot ambient electrons provide this energy in the form of collisional heating of plasmoid electrons, the expansion of a pellet plasmoid is expected to be a potent mechanism for the transfer of energy from electrons to ions on a time scale shorter than that of ion–electron thermalisation.

Physics↗
DOE OSTI2022

Self-organized patterns at the plasma–liquid anode interface in a helium glow discharge: temporal development and mechanisms

Self-organization at the plasma–liquid anode interface is a commonly observed phenomenon for atmospheric pressure glow plasmas, resulting in patterns with distinctive shapes such as circular ring, star-shaped, and gear-like structures, depending primarily on the discharge current and solution conductivity. Recent studies have shown that the electrode gap distance, solute used for liquid anode solution, and gas composition can also significantly impact pattern formation. Nonetheless, an overarching model or explanation of the key underlying mechanisms consistent with all experimentally observed trends is not yet reported. We propose a key underlying mechanism enabling pattern formation motivated by a detailed parametric study of pattern formation complemented by the temporal development of patterns and consistent with all observed trends. Pattern formation was observed to be on a time scale of 100 μs, similar to the time scales of gas heating and evaporation. It was found that a minimum water evaporation rate of (3.5 ± 0.5) × 10 –6 kg s –1 and reduced electric field in the positive column of 16.6 ± 0.4 Td is required for pattern formation in the investigated cases irrespective of solution conductivity and gas composition for NaCl solutions. Nonetheless, the presence of cations for which the corresponding metal atom has a low ionization energy was identified as a necessary condition for pattern formation. Furthermore, the reported results suggest that the presence of a small amount of metal atoms in the gas phase with low ionization energy enhances the overall ionization rate in the near anode region which triggers pattern formation.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2020

Gravitational Waves from Black Holes in Merging Ultra-Dwarf Galaxies

The origin of the black-hole:black-hole mergers discovered through gravitational waves with for example the LIGO/Virgo collaboration are a mystery. We investigate the idea that some of these black holes originate from the centers of extremely low-mass ultra-dwarf galaxies that have merged together in the distant past at $z>1$. Extrapolating the central black hole to stellar mass ratio suggests that the black holes in these mergers could arise from galaxies of masses $\sim 10^{5} - 10^{6}$ M$_{\odot}\,$. We investigate whether these galaxies merge enough, or too much, to be consistent with the observed GW rate of $\sim 9.7-101$ Gpc$^{-3}$ yr$^{-1}$ using the latest LIGO/Virgo results. We show that in the nearby universe the merger rate and number densities of ultra-dwarf galaxies are too low, by an order or magnitude, to produce these black hole mergers. However, by considering that the merger fraction, merger-time scales, and the number densities of low-mass galaxies all conspire at $z>1-1.5$ to increase the merger rate for these galaxies at higher redshifts we argue that it is possible that some of the observed GW events arise from BHs in the centers of low-mass galaxies. The major uncertainty in this calculation is the dynamical time-scales for black holes in low-mass galaxies. Our results however suggest a very long BH merger time-scale of 4-7 Gyr, consistent with an extended black hole merger history. Further simulations are needed to verify this possibility, however our theory can be tested by searching for host galaxies of gravitational wave events. Results from these searches would will put limits on dwarf galaxy mergers and/or the presence and formation mechanisms of black holes through PopIII stars in the lowest mass galaxies.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2020

Blazar variability power spectra from radio up to TeV photon energies: Mrk 421 and PKS 2155−304

ABSTRACT We present the results of the power spectral density (PSD) analysis for the blazars Mrk 421 and PKS 2155−304, using good-quality, densely sampled light curves at multiple frequencies, covering 17 decades of the electromagnetic spectrum, and variability time-scales from weeks up to a decade. The data were collected from publicly available archives of observatories at radio from Owens Valley Radio Observatory, optical and infrared (B, V, R, I, J, H, and Kbands), X-rays from the Swift and the Rossi X-ray Timing Explorer, high and very high energy (VHE) γ-rays from the Fermi and Very Energetic Radiation Imaging Telescope Array System as well as the High Energy Stereoscopic System. Our results are: (1) the power-law form of the variability power spectra at radio, infrared, and optical frequencies have slopes ∼1.8, indicative of random-walk-type noise processes; (2) the power-law form of the variability power spectra at higher frequencies, from X-rays to VHE γ-rays, however, have slopes ∼1.2, suggesting a flicker noise-type process; and (3) there is significantly more variability power at X-rays, high and VHE γ-rays on time-scales ≲ 100 d, as compared to lower energies. Our results do not easily fit into a simple model, in which a single compact emission zone is dominating the radiative output of the blazars across all the time-scales probed in our analysis. Instead, we argue that the frequency-dependent shape of the variability power spectra points out a more complex picture, with highly inhomogeneous outflow producing non-thermal emission over an extended, stratified volume.

Goyal, Arti↗
DOE OSTI2022

A multi-scale time-series dataset of anthropogenic heat from buildings in Los Angeles County

The dataset contains hourly Anthropogenic heat (AH) from buildings in Los Angeles County, based on weather data from 2018. The hourly AH is aggregated at three spatial resolutions: 450m x 450m grid, 12km x 12km grid, and census tract. The AH is broken down into three components: building envelope surface convection, heating, ventilation, and air conditioning (HVAC) system heat release, and zone exfiltration and exhaust air heat loss. The dataset is created with the physics-based EnergyPlus building energy models to calculate individual buildings' AH considering WRF-UCM simulated microclimate conditions. Please refer to the paper "A multi-scale time-series dataset of anthropogenic heat from buildings in Los Angeles County" for more information about the data generation workflow and the data validation procedure. The data set contains two folders: the "output_data" folder holds the simulation results (EP_output and EP_output_csv), building metadata (building_metadata.geojson and building_metadata.csv), aggregated heat emission and energy consumption time-series data (hourly_heat_energy), and geographical data (geo_data) associated with the GEOID referenced in heat and energy consumption data. The "input_data" folder contains the raw data used to generate files in the "output_data" folder as well as data sets used in the validation. The code repository (https://github.com/IMMM-SFA/xu_etal_2022_sdata) holds the processing scripts for data curation, validation, and visualization.

Energy↗
DOE OSTI2024

Implementing Superresolution of Nonstationary Tides with Wavelets: An Introduction to CWT_Multi

Abstract Tides are often nonstationary due to nonastronomical influences. Investigating variable tidal properties implies a trade-off between separating adjacent frequencies (using long analysis windows) and resolving their time variations (short analysis windows). Previous continuous wavelet transform (CWT) tidal methods resolved tidal species. Here, we present CWT_Multi, a MATLAB code that 1) uses CWT linearity (via the “response coefficient method”) to implement superresolution, i.e., resolving tidal constituents beyond the Rayleigh criterion; 2) provides a Munk–Hasselmann constituent selection criterion appropriate for superresolution; and 3) introduces an objective, time-variable form of inference (“dynamic inference”) based on time-varying data properties. CWT_Multi resolves tidal species on time scales of days, and multiple constituents per species with fortnightly filters. It outputs astronomical phase lags and admittances, analyzes multiple records, and provides power spectra of the signal(s), residual(s), and reconstruction(s); confidence limits; and signal-to-noise ratios. Artificial data and water levels from the Lower Columbia River Estuary (LCRE) and San Francisco Bay Delta (SFBD) are used to test CWT_Multi and compare it to harmonic analysis programs NS_Tide and UTide. CWT_Multi provides superior reconstruction, detiding, dynamic analysis utility, and time resolution of constituents (but with broader confidence limits). Dynamic inference resolves closely spaced constituents (like K 1 , S 1 , and P 1 ) on fortnightly time scales, quantifying impacts of diel power peaking (with a 24-h period, like S 1 ) on water levels in the LCRE. CWT_Multi also helps quantify the impacts of high flows and a salt barrier closing on tidal properties in the SFBD. On the other hand, CWT_Multi does not excel at prediction, and results depend on analysis details, as for any method applied to nonstationary data. Significance Statement Ocean tides, especially in coastal and estuarine systems, are often nonstationary, in the sense that the mean and standard deviation of tidal properties vary over time, usually in response to some nontidal process. We introduce here a MATLAB code, CWT_Multi, that uses wavelet transforms to resolve both tidal species and constituents on time scales from a few days to months. Our code accommodates multiple scalar time series and has typical tidal analysis features like constituent selection and inference, plus two forms of uncertainty analyses. It is flexible, allowing the user to adapt analysis properties to diverse datasets. CWT_Multi is applicable to many problems involving time-variable tides, including sea level rise, compound flooding, sediment transport, and wetland habitat analyses. Application to vector data is a straightforward extension, but further development of our uncertainty analysis is merited. Because nonstationary tidal analysis is rapidly advancing, we also define the features of a “well-formed” analysis code.

Lobo, Matthew↗
DOE OSTI2020

Effect of frequency and applied voltage of an atmospheric-pressure dielectric-barrier discharge on breakdown and hydroxyl-radical generation with a liquid electrode

This work examines the effect of the frequency and peak applied voltage on hydroxyl-radical generation in a dielectric-barrier plasma discharge between a metallic needle electrode and one electrode covered with dielectric. The authors examine a system that can expose up to 96 liquid samples in an automated fashion without human intervention beyond setting the initial software configuration. Then, hydroxylradical concentration, measured through coumarin fluorescence, was measured for 5 s plasma exposures generated under different highvoltage conditions with frequencies from 2 to 16 kHz and amplitudes from 4 to 9 kV. Their results show that an increase in frequency and/or applied voltage, within the range prescribed above and the limits of the high-voltage power supply, can yield up to a 150% increase in fluorescence with an equivalent hydroxyl-radical increase. Applications using typical previous methods, such as the Fenton Reaction, are limited in that they continuously generate hydroxyl radicals over millisecond and longer intervals. These results establish the electrical parameters that can now be applied to polymers, like proteins, which show three dimensional structures that are flexible and fluctuate on a microsecond and nanosecond time scale, with hydroxyl-radical generation on this time scale using this device. Additionally, plasma exposures may be optimized for a great variety of proteins, devices and techniques, where hydroxyl-radical generation is of utmost importance, reducing exposure time and potential subjection of samples to harmful side effects.

42 ENGINEERING↗
DOE OSTI2025

Porous Flow Modeling of Axial Gas Redistribution in Fragmented LWR Fuel Rods using MOOSE

Understanding how gas axially redistributes within fragmented fuel pellets is crucial for predicting the behavior of Light Water Reactor (LWR) fuel rods, particularly during transient and accidental scenarios. The time scale of this phenomenon plays a fundamental role in determining the progression and hazard of a Loss Of Coolant Accident (LOCA), especially when high burn-up fuel in a severe state of fragmentation is involved. Here, this study presents a Computational Fluid Dynamics (CFD) model developed within the Multiphysics Object-Oriented Simulation Environment (MOOSE) to predict the time-scale of plenum depressurization in Light-Water Reactor (LWR) fuel rods driven by axial gas transport through fragmented pellets. The model examines the effects of incorporating non-linearities in the friction term by comparing the results with experimental data. The experiment employed surrogate fuel rods containing pellets subjected to mechanical and/or thermal loadings to simulate various severity of cracking, and aimed at studying the influence of fuel conditions on axial gas redistribution. The results of this analysis indicate that under certain flow regime conditions - determined by the value of an equivalent Reynolds number - accounting for the non-linear friction term in Navier-Stokes equations guarantees better predictions for the time-scale of plenum depressurization. Also, the model enabled the simulation of the pressure decay by assigning distinct permeability values to each pellet instead of a single uniform value. Multiple simulations were run across all possible pellet position combinations, having each pellet assigned with values of permeability extracted from the experimental data. This allows to quantify the impact of the considering various non-uniform distributions of permeability on the dynamics of axial gas redistribution. The present work findings enhance the understanding of axial gas transport, and provide valuable insights for the integration of a model for predicting the axial gas redistribution during a LOCA scenario into the BISON fuel performance code.

11 - NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2021

Solvent absorption rate of perfluorosulphonic acid membranes towards understanding direct coating processes

Here we present a method for measurement of the rate of solvent absorption by perfluorosulfonic acid (PFSA) membranes using a force tensiometer. The method presented here can be used as a tool to understand solvent absorption and should provide a rationale for designing catalyst inks for direct coating processes since it is necessary to understand how the absorption rate – on a time scale of seconds to minutes – compares to the time scales of the coating process in order to minimize membrane swelling. This method allows for rapid screening of the absorption and swelling behavior of different solvents and mixtures. Using this method, the absorption of water/1-propanol mixtures were measured for three thicknesses of Nafion PFSA membrane – Nafion 1135, Nafion 115, and Nafion 117. We find that the absorption rate is dependent on the ratio of the solvents as well as the thickness of the membrane. The analysis indicates that the highest absorption rate occurs when the mass percentage of 1-propanol in the mixture is 50%, whereas the lowest rates are for pure water and 1-propanol. In addition, membrane distortion also occurs most quickly for the 50% 1-propanol mixture. Our results suggest that catalyst inks that are highly rich (=90%) in water or 1-propanol are likely best for direct coating as such formulations will minimize absorption and swelling.

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

Ultrafast X-ray Spectroscopy of Intersystem Crossing in Hexafluoroacetylacetone: Chromophore Photophysics and Spectral Changes in the Face of Electron-Withdrawing Groups

Intersystem crossings between singlet and triplet states represent a crucial relaxation pathway in photochemical processes. Herein, we probe the intersystem crossing in hexafluoro-acetylacetone with ultrafast X-ray transient absorption spectroscopy at the carbon K-edge. In this study, we observe the excited state dynamics following excitation with 266 nm UV light to the 1 ππ* (S 2 ) state with element and site-specificity using a broadband soft X-ray pulse produced by high harmonic generation. These results are compared to X-ray spectra computed from orbital optimized density functional theory methods. It is found that the electron-withdrawing fluorine atoms decongest the X-ray absorption spectrum by enhancing separation between features originating from different carbon atoms. This facilitates the elucidation of structural and electronic dynamics at the chromophore. The evolution of the core-to-valence resonances at the carbon K-edge reveals an ultrafast population transfer between the 1 nπ* (S 1 ) and 3 ππ* (T 1 ) states on a 1.6 ± 0.4 ps time scale, which is similar to the 1.5 ps time scale earlier observed for acetylacetone [ J. Am. Chem. Soc. 2017, 139, 16576—16583, DOI: 10.1021/jacs.7b07532]. It therefore appears that terminal fluorination has little influence on the intersystem crossing rate of the acetylacetone chromophore. In addition, the significant role of hydrogen-bond opened and twisted rotational isomers is elucidated in the excited state dynamics by comparison of the experimental transient X-ray spectra with theory.

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

Capturing Ring Opening in Photoexcited Enolic Acetylacetone upon Hydrogen Bond Dissociation by Ultrafast Electron Diffraction

Photoinduced biological and chemical reactions are often based on key structural transformations of a molecule driven across multiple electronic states. Acetylacetone (AcAc) is a prototypical system for complex chemical pathways involving several conical intersections (CI) and singlet–triplet intersystem crossings (ISC) characterized by distinct geometries. In the gas phase, AcAc is predominantly in a planar ring-like enolic form stabilized by a strong intramolecular O–H···O hydrogen bond. Following excitation into the S 2 (ππ*) state at 266 nm, acetylacetone undergoes rapid internal conversion followed by intersystem crossing. Such relaxation pathways are associated with structural changes including ring opening, deplanarization, and bond elongation. In this work, ultrafast electron diffraction (UED) at the SLAC MeV-UED setup is employed as a direct structural probe with a time resolution of 160 fs. Together with trajectory surface hopping simulations, analysis of the UED data provides a new perspective on the early time nuclear dynamics in acetylacetone. Specifically, AcAc is observed to undergo ring opening, deplanarization, and bond elongation all within the first 700 fs after photoexcitation. The monitored dynamics is associated mainly with the nuclear motion on the S 1 potential energy surface, formed after very rapid transfer from S 2 to S 1 , allowing AcAc to reach the conical intersection to intersystem crossing. Such time scales of nuclear motion are contrasted with the time scales of electronic transitions in AcAc that were previously characterized with spectroscopic methods, specifically internal conversion (<100 fs) and intersystem crossing (∼1.5 ps).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗