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At least 703 records · Page 39

Modified Fermi’s golden rule rate expressions

Fermi’s golden rule (FGR) serves as the basis for many expressions of spectroscopic observables and quantum transition rates. The utility of FGR has been demonstrated through decades of experimental confirmation. However, there still remain important cases where the evaluation of a FGR rate is ambiguous or ill-defined. Examples are cases where the rate has divergent terms due to the sparsity in the density of final states or time dependent fluctuations of system Hamiltonians. Strictly speaking, assumptions of FGR are no longer valid for such cases. However, it is still possible to define modified FGR rate expressions that are useful as effective rates. The resulting modified FGR rate expressions resolve a long standing ambiguity often encountered in using FGR and offer more reliable ways to model general rate processes. Finally, simple model calculations illustrate the utility and implications of new rate expressions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

High resolution X-ray spectroscopy of Supergiant HMXB 4U1700-37 during the compact object eclipse.

In this work, we present an analysis of the first observation of the iconic High Mass X-ray Binary 4U 1700-37 with the Chandra High Energy Transmission Gratings during an X-ray eclipse. The goal of the observation was to study the structure/physical conditions in the clumpy stellar wind through high resolution spectroscopy. We find that: a) emission line brightness from K shell transitions, corresponding to near neutral species, directly correlates with continuum illumination. However, these lines do not greatly diminish during eclipse. This is readily explained if fluorescence Kα emission comes from the bulk of the wind. b) The highly ionised Fe xxv and Fe xxvi Lyα diminish during eclipse. Thus, they must be produced in the vicinity of the compact object where log ξ > 3. c) to describe the emission line spectrum, the sum of two self consistent photo ionisation models with low ionisation (log ξ ~ -1) and high ionisation (log ξ ~2.4) is required. From their emission measures, the clump-to-interclump density ratio can be estimated to be nc/ni ~ 300. To fit the complex He-like Si xiii profile, the plasma requires a broadening with vbulk ~ 840 km s-1. Reproducing the observed r ≈ f line fluxes requires the addition of a third collisionally ionised plasma. d) Emission lines widths appear unresolved at the hetg gratings resolution with exception of Silicon. There is no clear radial segregation between (quasi)neutral and ionised species, consistent with cold wind clumps interspersed in a hot rarefied interclump medium.

79 ASTRONOMY AND ASTROPHYSICS↗

Laser Excitation of the Th-229 Nucleus

The 8.4 eV nuclear isomer state in Th-229 is resonantly excited in Th-doped CaF 2 crystals using a tabletop tunable laser system. A resonance fluorescence signal is observed in two crystals with different Th-229 dopant concentrations, while it is absent in a control experiment using Th-232. The nuclear resonance for the Th 4 + ions in Th: CaF 2 is measured at the wavelength 148.3821(5) nm, frequency 2020.409(7) THz, and the fluorescence lifetime in the crystal is 630(15) s, corresponding to an isomer half-life of 1740(50) s for a nucleus isolated in vacuum. These results pave the way toward Th-229 nuclear laser spectroscopy and realizing optical nuclear clocks. Published by the American Physical Society 2024

Physics↗

Synchrotron X-ray metrology of dopant distribution and oxidation state in high pressure CVD grown TM 2+ :ZnSe optical fibers

High pressure chemical vapor deposition (HPCVD) has shown to be a promising method for producing Cr 2+ :ZnSe and Fe 2+ :ZnSe mid-IR optical fiber lasers. The oxidation state of the dopants and their spatial homogeneity are critical for the characterization of effective fiber laser performance; however, this is challenging for small fiber cores and small doping concentrations. We demonstrate using synchrotron micro X-ray fluorescence (XRF) mapping to study the distribution of the dopants throughout the fiber cross-sections. Furthermore, we study the local chemical environment of these unique fiber structures using micro X-ray near edge absorption spectroscopy (XANES). Our study reveals that transition metal doped ZnSe deposited using HPCVD has nanoscale dopant aggregation although the material is chemically identical to the commercially produced diffusion doped laser crystals, as indicated by the presence +2 oxidation state of the dopants. This work demonstrates the power of synchrotron-based X-ray techniques for use as metrology tools for improving the performance of laser materials in fiber geometry.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Progress in laser-spectroscopic techniques for aerodynamic measurements - An overview

An overview is given of the capabilities and recent progress in laser-spectroscopic measurement techniques for use in aerodynamic test facilities and flight research vehicles. It includes a survey of the literature which is centered on this application of laser spectroscopy. The intended reader is the specialist in experimental fluid dynamics who is not intimately familiar with the physics or applications of laser spectroscopy. Thus, some discussion is also included of the nature of each laser-spectroscopic technique and the practical aspects of its use for aerodynamic measurements. The specific techniques reviewed include laser absorption, laser-induced fluorescence, laser Rayleigh scattering, and laser Raman scattering including spontaneous and coherent processes.

Mckenzie, Robert L.↗

Robust framework and software implementation for fast speciation mapping

One of the greatest benefits of synchrotron radiation is the ability to perform chemical speciation analysis through X-ray absorption spectroscopies (XAS). XAS imaging of large sample areas can be performed with either full-field or raster-scanning modalities. A common practice to reduce acquisition time while decreasing dose and/or increasing spatial resolution is to compare X-ray fluorescence images collected at a few diagnostic energies. In this work, several authors have used different multivariate data processing strategies to establish speciation maps. Furthermore, the theoretical aspects and assumptions that are often made in the analysis of these datasets are focused on. A robust framework is developed to perform speciation mapping in large bulk samples at high spatial resolution by comparison with known references. Two fully operational software implementations are provided: a user-friendly implementation within the MicroAnalysis Toolkit software, and a dedicated script developed under the R environment. The procedure is exemplified through the study of a cross section of a typical fossil specimen. Additionally, the algorithm provides accurate speciation and concentration mapping while decreasing the data collection time by typically two or three orders of magnitude compared with the collection of whole spectra at each pixel. Whereas acquisition of spectral datacubes on large areas leads to very high irradiation times and doses, which can considerably lengthen experiments and generate significant alteration of radiation-sensitive materials, this sparse excitation energy procedure brings the total irradiation dose greatly below radiation damage thresholds identified in previous studies. This approach is particularly adapted to the chemical study of heterogeneous radiation-sensitive samples encountered in environmental, material, and life sciences.

47 OTHER INSTRUMENTATION↗

Electron impact excitation and dissociation of N2 via the b 1Pi(u) state

Electron impact excitation of the b 1Pi(u) state in N2 plays a prominent role in the dissociation of the molecule and thus in the production of atomic nitrogen in planetary atmospheres. Electron impact excitation cross sections combined with electron-impact-induced fluorescence measurements can yield the corresponding dissociation cross sections. Serious discrepancies exist among excitation cross sections reported in the literature. To clarify the situation, these cross sections were measured at two impact energies using electron energy loss spectroscopy. The new results are in agreement with recent values deduced from optical measurements and fall midway between previous results which are too high or low by factors of 2.

Ratliff, J. M.↗

Carbon Monoxide Detector

Beckman Instruments, Inc. has introduced another technical approach to pollution detection which was used aboard Skylab. This technique, developed with Ames assistance is known as nondispersive infrared spectroscopy. Previous nondispersive analyzers could not selectively distinguish between water vapor and carbon monoxide, thus necessitating water removal by another device before measurement. These analyzers also were susceptible to vibrations and other problems. New instrument which stimulates fluorescent in two carbon monoxide isotopes in two sealed cells, eliminates these problems and increases sensitivity to a tenth of a part per million.

Source record↗

Large Volume Airborne Contamination Monitoring To Support Nuclear Processes' Deactivation and Decommissioning

Current D and D operations at Hanford have demonstrated a flaw in the current state of the art capability of defining airborne contamination boundaries - Airborne particulate emissions of Pu-239 from CM2H operations on the Hanford Pu Finishing Plant were detected well beyond areas controlled for airborne Pu, putting numerous workers at risk for radiological assimilations - Current air samplers and CAM systems were surveying insufficient volumes of air to accurately predict where respiratory protection was required - Hanford is located in a high radon environment, making air monitoring for alpha emitting actinides challenging in high alpha radon induced backgrounds. - Inexpensive HEPA based home and industrial air purifiers filter significantly higher volumes of air than commercially available continuous-air monitoring (CAM) systems. - Inexpensive models capable of filtered air volumes exceeding 1000 times that of a CAM. - Detector system can be built to detect x-rays generated from actinide decay. - Branching ratios of x-rays are 4 orders of magnitude more intense from Plutonium decay than its gamma emissions. - Detector system can be a low resolution systems, as x-ray region of interest is not terribly congested. - Detection systems evaluated will be designed based on slabs of NaI or pixelated NaI or CsI panels. - Simple graphical user interface software will be developed to operate the detection system. - Concept is to deploy some of these air-purifying systems in nonradiological areas around SRNL to confirm radon can be rejected with confidence. - Generate some filters contaminated with plutonium via electroplated Pu or lab generated simulated particles. - then deploy units in known airborne radiological environments to establish systems ability to accurately measure actinide based hot particles Lab analyses will follow up the system analyses to ensure hot particles were correctly identified. Analysis by Scintillation: - Application of scintillation media to the surface of the filters is being explored. - Evaluating slabs of ZnS(Ag), application of powdered ZnS(Cu) and spray on Perkin Elmer Enhance. - Scintillation events would then be digitized with a digital camera and quantified. - Comparing against sensitivity of a PMT or SiPD readout. - Currently evaluating a Thorlabs 8 Megapixel Monochrome Scientific CCD Camera, hermetically sealed cooled package with a wide angle lens. - Wide angle lens allows complete view of HEPA filter from 7 inches away. - Images taken of glow in the dark paint, as well as plutonium-induced fluorescence. - Plutonium was flamed mounted on a 1 inch diameter stainless steel planchet, covered with a layer of mylar and a section of scintillating ZnS obtained from Eljon. - Currently working on reducing signal-to-noise levels to boost sensitivity. - Dark box to hold contaminated or electroplated source covered filters under fabrication. Analysis by x-ray Spectroscopy: - Branching ratios for x-ray emissions from Plutonium isotopes are orders of magnitude more intense than gamma-ray emissions. - The nuclear databases are incomplete on the branching ratios of some of the isotopes. - Evaluating some custom built SrI2 x-ray spectrometers vs a conventional windowed NaI detector. - SrI2 detectors are carbon-composite-windowed 51 mm x 51 mm. - MCNP calculations to establish self absorbance of filter media on 17 keV x-ray. Radon Rejection: - Activated charcoal pre-filter acts as a Radon trap. - Adding a time lapse feature to camera to aid in radon rejection. SRS Plutonium Fuel Form D and D Operations: Currently deploying air sampler to D and D operation of Pu-238 facility at SRS to generate some field samples to analyze.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

A Combined Study Investigating the Insoluble and Soluble Organic Compounds in Category 3 Carbonaceous Itokawa Particles Recovered by the Hayabusa Mission

At the 3rd International Announcement of Opportunity (AO), we have been approved for five Category 3 carbonaceous Itokawa particles (RA-QD02-0012, RA-QD02-0078, RB-CV-0029, RB-CV-0080 and RB-QD04-0052) recovered by the first Hayabusa mission of JAXA. In this investigation, we aim to provide a comprehensive study to characterize and account for the presence of carbon-bearing phases as suggested by the initial Scanning Electron Microscopy (SEM) analysis carried out by JAXA at the curation facility, and to describe the mineralogical components of the particles. The insoluble organic content of Itokawa particle has been investigated with the use of micro-Raman spectroscopy by Kitajima and co-workers [1]. The Raman spectra of Itokawa particles show broad G- and D-bands typical of low temperature material which offers an interesting contrast to the high metamorphic grade (LL4-6) of the Itokawa parent body. Amino acid analysis has been conducted by Naraoka et al. [2] to study the soluble organic component of Itokawa particles, but since it was a preliminary study and thus did not have the opportunity to target on Category 3 carbonaceous particles, only terrestrial contaminants were identified. The investigation will be carried out in the following order prioritized according to the progressive damage the analytical techniques can induce: (1) micro-Raman spectrometry, (2) two-step laser mass spectrometry (micro-L2MS), (3) ultra-high performance liquid chromatography with fluorescence detection and time-of-flight mass spectrometry (LC-FD/ToF-MS), and optimally if we can recover the particles after wet chemistry analysis, we will mount the samples and perform (4) electron beam microscopy (SEM, electron back-scattered diffraction [EBSD]) and (5) carbon X-ray absorption near edge structure spectroscopy (C-XANES). We will begin the analytical procedures upon receiving the samples in September/October. This work will provide us with an understanding of the variety and origins of the carbon-bearing phases present in primitive solar system bodies from a direct sample-returned mission, which is less likely hampered by risks of terrestrial contamination as compared to meteorite finds and falls.

Chan, Q. H. S.↗

Measurement and reduction of Ar metastable densities by nitrogen admixing in electron beam-generated plasmas

Abstract Electron beam (e-beam) generated plasmas are useful for material processing applications such as deposition and etching because the plasmas deliver a large fluence of very low energy of ions to surfaces. Metastable species produced in the beam-region can also transport significant energy to the plasma periphery and surfaces. In this work, we have investigated the spatially resolved density of metastable Ar 1s 5 species produced in an Ar and Ar/N 2 e-beam generated plasma at pressures of 60–67 mTorr using laser-induced fluorescence (LIF). The experiments provide the first direct measure of absolute density and reduction of Ar 1s 5 in an e-beam generated plasma when argon is diluted with nitrogen. These results are consistent with previous predictions of numerical modeling and measurements using optical emission spectroscopy. The present spatially resolved LIF measurements directly quantify the reduction of Ar 1s 5 in the e-beam generated plasma by nitrogen admixing. This reduction was observed in the region of the electron beam and in the plasma periphery, where substrates are usually placed. For example, up to a threefold reduction of the density of Ar 1s 5 was measured when the argon background was diluted with 15.5% nitrogen at pressure of 60 mTorr. Ar 1s 5 reduction is attributed to excitation exchange with nitrogen molecules as well as the cooling of plasma electrons via inelastic collisions with nitrogen molecules.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Fe Kα XANES, Fe Kβ HERFD XANES and EPMA flank method determinations of the oxidation state of Fe in garnet

The ferric to total iron ratios (Fe 3+ /ΣFe) of garnets can be paired with thermodynamic mineral activity models to quantify the oxygen fugacity of garnet-bearing rocks. However, techniques with a high analytical and spatial resolution are necessary to distinguish differences in garnet Fe 3+ /ΣFe ratios at the percent level and to accurately measure garnets that are zoned or contain inclusions. We acquired conventional Fe Kα and high-resolution energy fluorescence detection (HERFD) Fe Kβ X-ray absorption near edge structure (XANES) spectra and electron microprobe flank method analyses on a suite of 27 peridotitic and eclogitic garnets with Fe 3+ /ΣFe ratios previously determined by Mössbauer spectroscopy to evaluate the precision of each technique. We examined variations in the energy and intensity of three XANES spectral features as a function of Fe 3+ /ΣFe ratios: 1) the intensity ratio of two-post edge features (I-ratio; Fe Kα only); 2) the energy of the Fe edge at 90% normalized intensity (E 0.9 ; Fe Kα only) and 3) the pre-edge centroid energy (Fe Kα and HERFD Fe Kβ). In accordance with previous work, we find the energies of garnet pre-edge centroids are relatively insensitive to Fe 3+ /ΣFe ratios. The I-ratios of peridotitic and eclogitic garnets are offset from each other at low Fe 3+ /ΣFe ratios (≤0.13); I-ratio garnet XANES calibrations are composition-specific. The E 0.9 feature is independent of garnet major element composition in spectra that have been corrected for the effects of self-absorption. We produce two Fe Kα garnet XANES calibrations based on variations in the E0.9 feature; one calibration with all garnet reference materials included (Fe 3+ /ΣFe up to 1.0; “all garnet calibration”) and another calibration specific to garnets with low Fe 3+ /ΣFe ratios (“low ferric calibration”). Fe 3+ /ΣFe ratios calculated from the mean of up to 25 flank method measurements on eight garnet reference materials fall within 4% absolute of a one-to-one correlation with Fe 3+ /ΣFe ratios measured by Mössbauer. The standard error of the mean Fe 3+ /ΣFe ratio calculated from flank method approaches the Mössbauer-determined Fe 3+ /ΣFe ratio within estimated error (3%) after three analyses. Flank method precision is enhanced at higher beam current; however, the precision of the flank method does not approach the precision of XANES under any microprobe analytical condition tested here. Garnet reference materials detailed here are available by request to the Smithsonian Institution.

58 GEOSCIENCES↗

A framework for quantitative analysis of spectral data in two channels

Simultaneous acquisition of emission intensity from two channels in dual-color fluorescence measurements can be used to determine the spectral properties of an emitter. We detail a method to extract quantitative information from dual-color measurements by considering two models: a single spectral component model for peak wavelength determination and a dual spectral component model for relative strength determination. The former model is useful for spectral characterization and establishing heterogeneity within an emitter species, while the latter model is useful for analyzing energy transfer efficiency. Both models are formalized to yield probability distributions that reflect uncertainties due to shot noise. We applied these analysis tools to single-particle measurements of CdSe/CdS quantum dots. Isolated emitters had narrow spectral-intensity distributions that reflected their static emission profiles and fluorescence stability. Small assemblies of mixed donor/acceptor particles exhibited dynamic behavior where emission configuration changes reveal different spectral characteristics due to energy transfer.

36 MATERIALS SCIENCE↗

Chemical state mapping of simulant Chernobyl lava-like fuel containing material using micro-focused synchrotron X-ray spectroscopy

Uranium speciation and redox behaviour is of critical importance in the nuclear fuel cycle. X-ray absorption near-edge spectroscopy (XANES) is commonly used to probe the oxidation state and speciation of uranium, and other elements, at the macroscopic and microscopic scale, within nuclear materials. Two-dimensional (2D) speciation maps, derived from microfocus X-ray fluorescence and XANES data, provide essential information on the spatial variation and gradients of the oxidation state of redox active elements such as uranium. In the present work, we elaborate and evaluate approaches to the construction of 2D speciation maps, in an effort to maximize sensitivity to the U oxidation state at the U L 3 -edge, applied to a suite of synthetic Chernobyl lava specimens. Our analysis shows that calibration of speciation maps can be improved by determination of the normalized X-ray absorption at excitation energies selected to maximize oxidation state contrast. The maps are calibrated to the normalized absorption of U L 3 XANES spectra of relevant reference compounds, modelled using a combination of arctangent and pseudo-Voigt functions (to represent the photoelectric absorption and multiple-scattering contributions). We validate this approach by microfocus X-ray diffraction and XANES analysis of points of interest, which afford average U oxidation states in excellent agreement with those estimated from the chemical state maps. This simple and easy-to-implement approach is general and transferrable, and will assist in the future analysis of real lava-like fuel-containing materials to understand their environmental degradation, which is a source of radioactive dust production within the Chernobyl shelter.

36 MATERIALS SCIENCE↗

Extraction and Characterization of Lipids from Salicornia virginica and Salicornia europaea

The lipid content from Salicornia virginica and Salicornia europaea is investigated. The plants are leafless halophytes with seeds contained in terminal nodes. The lipids, in the form of cell membranes and oil bodies that come directly from the node cells, are observed using fluorescence microscopy. Two extraction methods as well as the results of extracting from the seeds and from the entire nodes are described. Characterization of the fatty acid components of the lipids using Gas Chromatography in tandem with Mass Spectroscopy is also described. Comparisons are made between the two methods and between the two plant materials as lipid sources.

Kulis,Michael J.↗

Spectroscopy and electronic structure of the low-energy states of ThN

The electronic spectrum of ThN over the range 19,600–21,200 cm -1 is remarkably congested, showing at least twenty vibronic bands originating from the ground state zero-point level. Rotationally resolved spectra for eleven of these bands have been examined to probe the underlying reasons for the dense manifold of states. Dispersed fluorescence spectra and fluorescence decay lifetimes were measured to provide addition insights. Our experimental measurements were complemented by electronic structure calculations for the low-energy doublet and quartet states. The ab initio calculations yielded a density of excited states that was consistent with the congested spectrum. These states were derived from the formal configurations Th 3+ (6d)N 3- , Th 2+ (7s 2 )N 2- (2p 5 ) and Th 2+ (7s6d)N 2 -(2p 5 ). The calculations indicated that the rotational and vibrational constants would be characteristic of the electronic configurations. This prediction was not borne out by the experimental data, suggesting that the full range of inter-configurational state interactions were not captured by the computational model.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Probing Nanocrystal Optical Properties in the Limit of Single Nanocrystals

The Bawendi lab has been at the forefront of the synthesis and characterization of the fundamental photo-physics of quantum confined systems for the past three decades. During this DoE project, our progress has been enabled by both our expertise in single nanocrystal (NC) photoluminescence (PL) spectroscopy as well as our extensive knowledge of the synthetic optimization of various NC semiconductors - all of this forming an efficient feedback loop between characterization and synthesis. Our research in this project has focused on the development and application of novel single emitter optical tools for the characterization of colloidal quantum dots (CQDs) which are semiconducting NCs with size-tunable quantum confined electronic structure. CQDs have had a significant commercial impact as display technologies. They are also commercially available as fluorescent biological markers. CQDs are being investigated as a potential material for photovoltaic or optical sensing applications and as emerging optical quantum materials. We have focused on the fundamental understanding of the optical properties of NCs through the development of novel spectroscopic methods at the single emitter level, including understanding how synthetic and environmental heterogeneities influence NC properties. A major advance in our research has been the development of novel photon resolved correlation spectroscopies that allow us to extract the physics of photo-excited single NCs with unprecedented time and spectral resolution from the photon stream of individual NCs.

36 MATERIALS SCIENCE↗

Determination of Chlorophyll Content in Selected Grass Communities of Krkonoše Mts. Tundra Based on Laboratory Spectroscopy and Aerial Hyperspectral Data

The study focuses on the determination of chlorophyll content in four prevailing grasses in the relict arctic-alpine tundra located in the Krkonoše Mountains National Park, Czech Republic. We compared two methods for determination of leaf chlorophyll content (LCC) – spectrophotometric determination in the laboratory, and the LCC assessed by fluorescence portable chlorophyll meter CCM-300. Relationships were established between the LCCs and vegetation indices calculated from leaf spectra acquired with contact probe coupled with an ASD FieldSpec4 Wide-Res spectroradiometer. Canopy chlorophyll contents (CCC) were computed from the LCCs and green leaf area index (LAI), and modelled based on the field spectra measured by the spectroradiometer and the hyperspectral images acquired by Headwall Nano-Hyperspec® mounted on the DJI Matrice 600 Pro drone. The calculations are performed on datasets acquired in June, July and August 2020 together and separately for species and months. In general, the correlations based on June datasets work the best at both levels: median R 2 for all indices was 0.52 for all species together at leaf level and median R 2 = 0.47 at the canopy level (vegetation indices computed from field spectra). Canopy chlorophyll content map was created based on the results of stepwise multiple linear regression. The R 2 was 0.42 when using four wavelengths from the red and red edge spectral region. We attribute the weak model performance to a combination of several factors: leaf structure may bias LCC from laboratory measurements, effects of LAI variability on CCC, and the sampling design, probably not covering the whole phenology equally for all studied species.

L. Cervena↗