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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 289 records · Page 16
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Transfer and Flushing Evaluation for Potential Precipitated Solids in the 241-AP-106 to EMF Transfer Pipeline for DFLAW

Waste transfer pipeline flushing is necessary to maintain pipeline performance, but added flush fluid increases the nuclear waste inventory. During the Direct Feed Low-Activity Waste (DFLAW) mission, waste transfer lines from the Interim Low-Activity Waste Storage Tank (i.e., 241-AP-106) to the Hanford Waste Treatment and Immobilization Plant (WTP) Low-Activity Waste (LAW) Facility must have the capability of being flushed to prevent accumulation of solids and to mitigate corrosion concerns. Operational experience at Hanford has shown that the solids precipitation occurs during processing operations from dilute Hanford liquids. Pacific Northwest National Laboratory was requested to evaluate the potential precipitated solid particle transport and flushing operational capabilities of the AP-106 through the Effluent Management Facility (EMF) low-point drain LAW feed pipeline. The evaluation results do not provide operational requirements, but rather provide a scoping basis for understanding the potential operational significance of solids precipitation in the pipeline. The salt and aluminum phase solids most likely to precipitate from the LAW feeds during cooling, evaporation, or mixing have particle densities that are estimated to range from 1.62 to 2.78 g/mL and a spherical particle size range of 8 to 2100 μm, depending on the solid phase considered. Application of the method to calculate the critical deposition velocity required by TFC-ENG-STD-26 at conservatively bounding estimates for the solids concentrations demonstrates that potentially precipitated solids may deposit on the bottom of the transfer pipe invert at the lower LAW feed pipeline flow rate, but the upper LAW feed pipeline flow rate will likely prevent deposition. The system pressure limit for the AP-106 through the EMF low-point drain LAW feed pipeline likely exceeds any pressure loss at a calculated critical deposition velocity even for the most adverse potential precipitated solid. However, should solids settle as a result of no-flow conditions, the flow capabilities of the AP-106 through the EMF low-point drain LAW feed pipeline are shown, based on the available literature, to be potentially inadequate for effective flushing operations to remove solids, even at solids concentrations below the maximum specified for LAW feed. Thus, stepwise solids accumulations over multiple transfers may be an issue, and eventual line plugging may occur. Further inadequacies may potentially be realized should the cohesive nature of certain precipitates be accounted for.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2020

Multi-Scale Simulation of Wind Farm Performance during a Frontal Passage

Predicting the response of wind farms to changing flow conditions is necessary for optimal design and operation. Here in this work, simulation and analysis of a frontal passage through a utility scale wind farm is achieved for the first time using a seamless multi-scale modeling approach. A generalized actuator disk (GAD) wind turbine model is used to represent turbine–flow interaction, and results are compared to novel radar observations during the frontal passage. The Weather Research and Forecasting (WRF) model is employed with a nested grid setup that allows for coupling between multi-scale atmospheric conditions and turbine response. Starting with mesoscale forcing, the atmosphere is dynamically downscaled to the region of interest, where the interaction between turbulent flows and individual wind turbines is simulated with 10 m grid spacing. Several improvements are made to the GAD model to mimic realistic turbine operation, including a yawing capability and a power output calculation. Ultimately, the model is able to capture both the dynamics of the frontal passage and the turbine response; predictions show good agreement with observed background velocity, turbine wake structure, and power output after accounting for a phase shift in the mesoscale forcing. This study demonstrates the utility of the WRF-GAD model framework for simulating wind farm performance under complex atmospheric conditions.

17 WIND ENERGY↗
DOE OSTI2022

Heat pulse testing at monitoring wells to estimate subsurface fluid velocities in geological CO 2 storage

Monitoring the injected CO 2 during geological CO 2 storage (GCS) is essential to assure containment and identify CO 2 leakage. Here in this work, a new approach is introduced to estimate the evolution of the downhole fluid velocity at a monitoring well and identify CO 2 arrival time using in-well heat pulse/tracer test. The proposed technique involves using a downhole heater to generate a series of heat pulses and measuring their corresponding temperature response. The surface temperature of the downhole heater is controlled by the supplied electrical power and the heat loss by convection to the surroundings. Convective heat transfer is well described using Newton's law of cooling in which the temperature difference between the heater and the surrounding fluids drives the heat transfer, for which the convection heat transfer coefficient (h) controls the magnitude of heat loss. Among various factors that control h, it depends on the type of the flowing fluid and its velocity. Through analyzing the measured temperature at different heat pulses, the changes in h - due to mobilization of the in-situ brine or CO 2 arrival - can be estimated. Consequently, the velocity of the flowing fluid across the heater can be obtained. Since heat transfer by convection is sensitive to the type of the surrounding fluid, intrusion of CO 2 can be detected from the relatively higher surface temperature obtained at CO 2 arrival. Churchill and Bernstein (1977)'s correlation is adopted to estimate the change of fluid velocity in terms of the change in h. To demonstrate the validity of the proposed technique, the results are applied and validated against those of COMSOL Multiphysics simulation tool for single-phase brine (before CO 2 arrival) and single-phase CO 2 (after CO 2 arrival). The observed temperature heating is sensitive to the flowing fluid velocity and fluid type. The temperature signal observed at CO 2 arrival is large and easily detectable using temperature monitoring tool which provides reliable indication for tracking CO 2 arrival at monitoring wells compared with passive temperature monitoring. The results obtained using the proposed technique agree very well with the numerical results obtained from the simulation tool with a maximum estimation error of 7 percent.

02 PETROLEUM↗
DOE OSTI2022

Divergence of Velocity Fields in Electrochemical Systems

The passage of current through electrochemical systems results in the development of concentration gradients in the electrolytic phase that can be modeled using concentrated solution theory. Application of this theory requires knowledge of three concentration-dependent transport coefficients, which are often taken to be conductivity, diffusion coefficient, and the cation transference number with respect to the solvent velocity. The governing diffusion equation for molar concentration contains two additional terms - the thermodynamic factor which is related to activity of the electrolytic species and the solvent velocity. The main advance in this paper is the derivation of an expression for the divergence of the solvent velocity. Solving this equation requires knowledge of the partial molar volume of the electrolyte. Analogous expressions are derived for the mass average and molar average velocities. These velocities occur naturally in the diffusion equation if concentration is expressed as weight fraction and mole fraction of the electrolytic species, respectively.

diffusion↗
DOE OSTI2023

Particle inertial effects on radar Doppler spectra simulation

Abstract. Radar Doppler spectra observations provide a wealth of information about cloud and precipitation microphysics and dynamics. The interpretation of these measurements depends on our ability to simulate these observations accurately using a forward model. The effect of small-scale turbulence on the radar Doppler spectra shape has been traditionally treated by implementing the convolution process on the hydrometeor reflectivity spectrum and environmental turbulence. This approach assumes that all the particles in the radar sampling volume respond the same to turbulent-scale velocity fluctuations and neglects the particle inertial effect. Here, we investigate the inertial effects of liquid-phase particles on the forward modeled radar Doppler spectra. A physics-based simulation (PBS) is developed to demonstrate that big droplets, with large inertia, are unable to follow the rapid change of the velocity field in a turbulent environment. These findings are incorporated into a new radar Doppler spectra simulator. Comparison between the traditional and newly formulated radar Doppler spectra simulators indicates that the conventional simulator leads to an unrealistic broadening of the spectrum, especially in a strong turbulent environment. This study provides clear evidence to illustrate the droplet inertial effect on radar Doppler spectrum and develops a physics-based simulator framework to accurately emulate the Doppler spectrum for a given droplet size distribution (DSD) in a turbulence field. The proposed simulator has various potential applications for the cloud and precipitation studies, and it provides a valuable tool to decode the cloud microphysical and dynamical properties from Doppler radar observation.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2021

Scheduling strategies for the ESPRESSO follow-up of TESS targets

ABSTRACT Radial-velocity follow-up of stars harbouring transiting planets detected by TESS is expected to require very large amounts of expensive telescope time in the next few years. Therefore, scheduling strategies should be implemented to maximize the amount of information gathered about the target planetary systems. We consider myopic and non-myopic versions of a novel uniform-in-phase scheduler, as well as a random scheduler, and compare these scheduling strategies with respect to the bias, accuracy and precision achieved in recovering the mass and orbital parameters of transiting and non-transiting planets. This comparison is carried out based on realistic simulations of radial-velocity follow-up with ESPRESSO of a sample of 50 TESS target stars, with simulated planetary systems containing at least one transiting planet with a radius below 4R⊕. Radial-velocity data sets were generated under reasonable assumptions about their noise component, including that resulting from stellar activity, and analysed using a fully Bayesian methodology. We find the random scheduler leads to a more biased, less accurate, and less precise, estimation of the mass of the transiting exoplanets. No significant differences are found between the results of the myopic and non-myopic implementations of the uniform-in-phase scheduler. With only about 22 radial velocity measurements per data set, our novel uniform-in-phase scheduler enables an unbiased (at the level of 1 per cent) measurement of the masses of the transiting planets, while keeping the average relative accuracy and precision around 16 per cent and 23 per cent, respectively. The number of non-transiting planets detected is similar for all the scheduling strategies considered, as well as the bias, accuracy and precision with which their masses and orbital parameters are recovered.

Cabona, L.↗
DOE OSTI2020

X-ray Phase Contrast Imaging of the Impact of Multiple HMX Particles in a Polymeric Matrix

The initiation of high explosives (HEs) under shock loading lacks a comprehensive understanding: particularly at the particle scale. One common explanation is the hot spot theory, which suggests that energy in the material resulting from the impact event is localized in a small area causing an increase in temperature that can lead to ignition. This study focuses on the response of HMX particles (a common HE) within a polymer matrix (Sylgard-184 (R)), a simplified example of a polymer-bound explosive (PBX). These PBXs consist of multiple HMX particles in a single polymer-bound sample. A light gas gun was used to load the samples at impact velocities above 400 m/s. The impact events were visualized using X-ray phase-contrast imaging (PCI) allowing real-time observation of the impact event. The experiment used two different types of samples (multi-particle and two crystals) and found evidence of cracking and debonding in both sample types. Additionally, it was found that the multiple particle samples showed similar evidence of damage at lower velocities than that of single particle samples. This is an expected result as the multiple particles add additional interfaces for stress concentration and frictional heating.

42 ENGINEERING↗
DOE OSTI2021

Multiphase phase-field approach for solid–solid phase transformations via propagating interfacial phase in HMX

In this study, a thermodynamically consistent multiphase phase-field theory has been formulated to describe temperature-induced solid–solid phase transformations via an interfacial phase. This theory satisfies all thermodynamic equilibrium and stability conditions. It allows us to formulate the analytical solutions of the interface profile, energy, width, and velocity for each of the propagating solid–melt and solid–solid interfaces. The formation of the intermediate melt during solid–solid phase transformation has been studied hundreds of degrees below melting temperature in the HMX energetic crystal. The effect of the penalizing term in the phase-field model and two nanoscale material parameters on the appearance and degree of disordering of intermediate melt has been analyzed for the non-equilibrium interface. The developed approach is applicable to phase transitions in geological, pharmaceutical, ferroelectric, colloidal, and superhard materials where phase transformations occur via the intermediate phase.

Roy, Arunabha M. (ORCID:000000034790726X)↗
DOE OSTI2025

Detection of multi-modal Doppler spectra – Part 1: Establishing characteristic signals in radar moment data

Vertically pointing millimeter-wavelength radars provide a wealth of information about cloud and precipitation particle properties. Doppler spectral data can inform on how particles of varying vertical velocities contribute to the total backscattered power observed. It is more computationally cost effective to process moment data instead of spectra data, but doing so leaves valuable information on the cutting room floor. To confidently identify a multi-modal spectra event, in which two or more modes are present within a layer, Doppler spectral data are essential. This means long-term identification of layers featuring multi-modal spectra can be cost prohibitive. To address this, we explore three multi-modal spectra cases from winter precipitation events to determine characteristic signatures of these layers in the moment data averaged over short time periods (∼ 145 s) and explore how these layers differ from the rest of the vertical profiles. We find that the mean spectrum width and the standard deviation of mean Doppler velocity can be used to determine whether or not a layer is multi-modal. In particular, multi-modal layers in mixed-phase and ice clouds feature larger mean spectrum width (exceeding 0.17 m s −1 ) and smaller standard deviation of the mean Doppler velocity (below 0.1 m s −1 ). In Part 1 of this study, the identification criteria and methods are described. In Part 2 (Wugofski and Kumjian, 2025), we perform a verification of the method for three years of vertically pointing radar data, and explore the meteorological conditions associated with identified multi-modal spectral events.

Wugofski, Sarah [Pennsylvania State Univ., Univers↗
DOE OSTI2020

Final Report for DTRA Project "High-resolution Velocity and Attenuation Model for Eastern Mediterranean/Mideast Region"

The overall goal of this project is to build a high-resolution velocity and attenuation model for a region spanning from the eastern Mediterranean Sea and extending eastward into the Middle East. Phase I of this project, covered in this report, focuses on the analysis of the SHDAS array, updated dispersion and amplitude measurements, development of surface wave group velocity models, and construction of a preliminary 1-degree, velocity-only model for the study region. These will be discussed in turn.

58 GEOSCIENCES↗
DOE OSTI2026

X-Band Scanning ARM Precipitation Radar, CF/Radial Formatted, Quality Controlled

The X-band Scanning ARM Precipitation Radar (X-SAPR) is an X-band dual-polarization Doppler weather radar. The X-SAPR operates in a simultaneous transmit and receive (STAR) mode, meaning that the transmit signal is split so that power is transmitted on both horizontal and vertical polarizations at the same time. The X-SAPR transmitter is a 200 kW (peak power) magnetron. The receiver is based upon the Vaisala RVP-900 and runs Vaisala’s IRIS software. In addition to the first three Doppler moments (reflectivity, radial velocity, and spectra width), the X-SAPR also provides differential reflectivity, correlation coefficient, and specific differential phases. The dual-polarization variables enable estimates of rainfall rates and identification of precipitation types. At the Southern Great Plains site, three X-SAPRs surround the Central Facility, allowing the use of multi-Doppler velocity retrievals to estimate wind fields.

xsaprcfrqc↗
DOE OSTI2022

Assessing free tropospheric quasi-equilibrium for different GCM resolutions using a cloud-resolving model simulation of tropical convection

Abstract This study examines the free-tropospheric quasi-equilibrium at different global climate model (GCM) resolutions using the simulation of tropical convection by a cloud-resolving model during the Tropical Western Pacific International Cloud Experiment. The simulated dynamic and thermodynamic fields within the model domain are averaged over subdomains of different sizes equivalent to different GCM resolutions. These coarse-grained fields are then used to compute CAPE and its change with time, and their relationships with simulated convection. Results show that CAPE change with time is controlled predominantly by variations of thermodynamic properties in the planetary boundary layer for all subdomain sizes ranging from 64 to 4 km. Lag correlation analysis shows that CAPE generation by the free-tropospheric dynamical advection (dCAPE ls ) leads convective precipitation but is in phase with convective mass flux at 600 mb and 500 mb vertical velocity for all subdomain sizes. However, the correlation coefficients and regression slopes decrease as the subdomain size decreases for subdomain sizes smaller than 16 km. This is probably due to increased randomness of convection and more scale-dependence of the relationships when the subdomain size reaches the grey zone. By examining the sensitivity of the relationships of convection with dCAPE ls to temporal scales in different subdomain size, it shows that the quasi-equilibrium between dCAPE ls and convection holds well for timescales of 30 min or longer at all subdomain sizes. These results suggest that the free tropospheric quasi-equilibrium assumption may still be useable even for GCM resolutions in the grey zone.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2021

Adiabatic quantum decoherence in many non-interacting subsystems induced by the coupling with a common boson bath

Highlights: • System–environment quantum correlation: a main solid state NMR decoherence channel. • Non-separable system–environment model yields realistic spin decoherence rates. • New open quantum system approach explains irreversible decay of refocused NMR echoes. • Adiabatic quantum decoherence is inherently irreversible and eigen-selective. This work addresses adiabatic quantum decoherence of many-body spin systems coupled with a boson field in the framework of open quantum systems theory. We generalize the traditional spin-boson model by considering a system–environment interaction Hamiltonian that represents a partition of non-interacting subsystems and highlights the collective correlation that appears exclusively due to the coupling with a common environment. Remarkably, this simple, exactly solvable model encompasses relevant aspects of a many-body open quantum system and features the subtle quantum effects that arise when the size scales up to a macroscopic level. We derive an analytical expression for the time dependence of the density matrix elements (in the preferred basis) without assuming coarse-graining. The resulting decoherence function is eigen-selective and is a complex exponential whose exponent has a real part that introduces a decay similar to that in the spin-boson model. On the contrary, the imaginary part depends on the quantum numbers and geometry of the whole partition and does not reflect the system temperature. Motivated by decoherence in solid-state NMR, and in search of realistic numerical estimations, we apply the theoretical results to a partition of dipole-coupled spin pairs in contact with a common phonon bath, using typical parameters of hydrated salts. The proposal allows estimating the decoherence time scale in terms of the system physical constants: sound velocity and eigenvalue distribution width. As a significant novelty, the decoherence function phase depends on the eigenvalue distribution throughout the sample. It plays the leading role, overshadowing the mechanism associated with the bath thermal state. Finally, we apply the formalism to describe decoherence in the “magic echo” NMR reversal experiment. We find that the system–environment correlation explains the origin of irreversibility, and both the decoherence rate value and its dependence on the dipolar frequency, are remarkably similar to the experiment.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2021

Experimental study of flash boiling spray with isooctane, hexane, ethanol and their binary mixtures

The main goal of this study is to understand the effect of fuel properties on flash boiling sprays using multi-hole injectors. Macroscopic characteristics were investigated using Diffused Backlight Imaging (DBI) and quantified with liquid penetration length and spray angles. Phase Doppler Anemometry (PDA) was applied to measure the droplet size and velocity. Behaviors of spray with three single-component fuels (isooctane, hexane, ethanol) under different ambient pressures (100 kPa, 80 kPa, 50 kPa, 22 kPa) as well as their binary mixtures under different blend ratios (10%, 30%, 85%) were reported and analyzed. The results showed that adding ethanol or hexane to isooctane could both promote flash boiling by increasing the overall vapor pressure thus superheated degree. Under mixing ratios of 10% and 30%, sprays with ethanol blends showed more severe flash boiling comparing with sprays with hexane blends. Shorter liquid penetration and better liquid dispersion have been observed. Comparing with isooctane spray, the droplet size continuously decreased with increasing hexane content due to enhanced breakup and faster vaporization. Sprays with ethanol mixtures showed a different trend. Noticeable droplet size reduction has been observed for spray with 10% ethanol content. However, droplet size did not further decrease with higher blend ratios regardless of higher flash boiling intensity. Such observations indicate severe vaporization inhibition caused by the high latent heat of vaporization of ethanol. For sprays with all test fuels, collapsing occurred when the pressure ratio of ambient pressure to saturation pressure (Rp) dropped below 0.3.

03 NATURAL GAS↗
DOE OSTI2022

Ultrasonic nondestructive diagnosis of lithium-ion batteries with multiple frequencies

Accurately estimating the state of charge (SoC) in battery management systems (BMSs) requires the measurement of numerous parameters and advanced algorithms. This work studies multifrequency ultrasonic waves to estimate the SoC of Li-ion batteries by sensing the material changes during charge/discharge. A pouch-type LiNi 0.6 Mn 0.2 Co 0.2 O 2 (NMC622) graphite battery cell is designed and fabricated with a capacity of 2.4 Ah. Different ultrasonic testing setups are explored to determine the optimal testing parameters for the battery. An ultrasonic monitoring system is developed to monitor the battery during charge/discharge at 750 kHz, 1 MHz, and 1.5 MHz. Signal processing algorithms are proposed for extracting three ultrasonic features—amplitude, wave velocity, and attenuation. In a three-cycle test, the amplitude histories do not show clear correlations with the SoC. The wave velocities of all three frequencies have an approximately linear relationship with the SoC, which can be used for SoC estimation. Hysteresis behavior is observed for the wave velocity in terms of a larger slope in the discharge process and velocity drop after a close charge/discharge cycle. The wave attenuation is able to capture the material phase transitions during charge/discharge.

25 ENERGY STORAGE↗
DOE OSTI2020

Modal dynamics of high-frequency transverse combustion instabilities

This paper investigates the modal dynamics of self-excited high frequency transverse instabilities in a multi-nozzle, swirl-stabilized can combustor. It utilizes results from multiple pressure sensors to decompose the disturbance into clockwise (CW) and counter-clockwise (CCW) waves, enabling a reconstruction of the pressure amplitude, phase, anti-nodal line location, and spin ratio. While these types of decompositions have been demonstrated on small scale combustors, particularly annular combustors, this is the first study to analyze these results for a high power, multi-nozzle can combustor. Its particular focus is in characterizing the system evolution in phase space and the nature of the system attractors under linearly unstable conditions; results are presented in spin ratio-phase difference space, so that limit cycle oscillations appear as fixed points. Results are shown for conditions where three different attractors dominate (standing, CW, and CCW) but are taken for very long time periods (~50,000 cycles) so that the system's interaction with these attractors can be observed. For the standing mode-dominated case, the phase portrait shows spiral trajectories converging to a single fixed point. For the spinning mode dominated cases, however, multiple fixed points and saddle points were observed, and the trajectories showed a more complicated structure. It was also shown that even though the CW mode is dominant, this mode intermittently switches to standing or CCW modes for short period. These results suggest that the strength of each attractor depends on test conditions and that random noise stochastically perturbs the system so that large regions of the phase space are explored. Lastly, one interesting observation is that the angular velocity of the anti-nodal line linearly varies with the spin ratio under standing-mode dominant conditions.

42 ENGINEERING↗
DOE OSTI2022

Stability of a Mixed–Valence Hydrous Iron–Rich Oxide: Implications for Water Storage and Dynamics in the Deep Lower Mantle

Incorporation of water into mantle compositions can have significant effects on the phase relations in the systems. Here, we synthesized an iron-rich hexagonal hydrous phase (referred to as "HH1-phase") under the high pressure-temperature (P-T) conditions of the deep lower mantle and determined the crystal structure of the HH1-phase at 79 GPa using the multigrain crystallography method. The chemical formula obtained was Fe 12.76 O 18 H x (x ~ to 4.5) in the Fe-O-H system. To demonstrate the role of HH1-phase for water storage in multicomponent systems relevant to mantle compositions, we investigated the stability of HH1-phase in both MgO-rich pyrolitic and SiO 2 -rich basaltic compositions. Our results indicate that the HH1-phase serves as major water storage in a pyrolitic composition, whereas the Al-rich CaCl 2 -type δ-phase and SiO 2 phase are major water storage phases in a SiO 2 -rich basaltic composition. Incorporation of considerable amounts of SiO 2 , MgO, and Al 2 O 3 into the HH1-phase expands its stability field from 98 GPa in the Fe-Al-O-H system to at least 108 GPa (corresponding to similar to 2,400 km depth) in the Mg-Si-Al-Fe-O-H system. Plumes of hot upwelling rock rooted at the base of the lower mantle have been proposed as a possible origin of hotspot volcanoes. The hydrous Fe-rich HH1-phase, if included into the material of upwelling plumes, will decompose on its rising to the upper part of the lower mantle and release water. Our results should provide constraints on water storage in the deep lower mantle and have implications for deep mantle dynamics.

58 GEOSCIENCES↗
DOE OSTI2020

Looking at the bigger picture: Identifying the photoproducts of pyruvic acid at 193 nm

Here, photodissociation of pyruvic acid (PA) was studied in the gas-phase at 193 nm using two complementary techniques. The time-sliced velocity map imaging arrangement was used to determine kinetic energy release distributions of fragments and estimate dissociation timescales. The multiplexed photoionization mass spectrometer setup was used to identify and quantify photoproducts, including isomers and free radicals, by their mass-to-charge ratios, photoionization spectra, and kinetic time profiles. Using these two techniques, it is possible to observe the major dissociation products of PA photodissociation: CO 2 , CO, H, OH, HCO, CH 2 CO, CH 3 CO, and CH 3 . Acetaldehyde and vinyl alcohol are minor primary photoproducts at 193 nm, but products that are known to arise from their unimolecular dissociation, such as HCO, H 2 CO, and CH 4 , are identified and quantified. A multivariate analysis that takes into account the yields of the observed products and assumes a set of feasible primary dissociation reactions provides a reasonable description of the photoinitiated chemistry of PA despite the necessary simplifications caused by the complexity of the dissociation. These experiments offer the first comprehensive description of the dissociation pathways of PA initiated on the S 3 excited state. Most of the observed products and yields are rationalized on the basis of three reaction mechanisms: (i) decarboxylation terminating in CO 2 + other primary products (~50%); (ii) Norrish type I dissociation typical of carbonyls (~30%); and (iii) O—H and C—H bond fission reactions generating the H atom (~10%). The analysis shows that most of the dissociation reactions create more than two products. This observation is not surprising considering the high excitation energy (~51 800 cm –1 ) and fairly low energy required for dissociation of PA. We find that two-body fragmentation processes yielding CO 2 are minor, and the expected, unstable primary co-fragment, methylhydroxycarbene, is not observed because it probably undergoes fast secondary dissociation and/or isomerization. Norrish type I dissociation pathways generate OH and only small yields of CH 3 CO and HOCO, which have low dissociation energies and further decompose via three-body fragmentation processes. Experiments with d 1 -PA (CH 3 COCOOD) support the interpretations. The dissociation on S 3 is fast, as indicated by the products’ recoil angular anisotropy, but the roles of internal conversion and intersystem crossing to lower states are yet to be determined.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗