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At least 37 records · Page 2

Precise laser frequency scanning using frequency-synthesized optical frequency sidebands - Application to isotope shifts and hyperfine structure of mercury

Based on an efficient broadband electrooptic modulator producing RF optical sidebands locked to a stable cavity, a tunable dye laser can be scanned under computer control with frequency-synthesizer precision. Cavity drift is suppressed in software by using a strong feature in the spectrum for stabilization. Mercury isotope shifts are measured with a reproducibility of about 50 kHz. This accuracy of about 1/300 of the linewidth illustrates the power of the technique. Derived hyperfine-structure constants are compared with previous atomic-beam data.

Rayman, M. D.↗

The influence of laser energy on deuterium emission characteristics from a Zircaloy-4 plasma

Laser-produced plasma coupled with optical emission spectroscopy (OES) is a promising technique for detecting certain isotopes, with unique capabilities such as standoff and rapid detection and minimal to no sample preparation requirements. The key figure-of-merit for isotopic analysis using optical spectroscopy tools is the linewidth relative to the isotope shift. Although the isotopes of hydrogen (1H, 2H, and 3H) possess large isotopic shifts (1H–2H ≈ 180 pm, 1H–3H ≈ 240 pm), being a light element, the H transitions are susceptible to various broadening mechanisms in the plasma environment. One of the critical parameters that influence the linewidth of a transition in an LPP is the incident laser energy. In the present study, we evaluated the role of laser energy on plume expansion dynamics, deuterium emission intensity, and linewidth in a nanosecond laser-produced Zircaloy-4 plasma. The changes in 2Hα emission intensity and linewidth were investigated for varying laser fluence and time after plasma onset. Spatially resolved and spatially integrated OES were performed and compared to investigate the emission spectral features and linewidth of 2Hα. Monochromatic two-dimensional time-resolved imaging was also performed to understand the morphology of the deuterium and protium emission relative to all species in the plume. Our results showed that 1Hα and 2Hα emissions predominantly occur closer to the target. Measurements of 2Hα linewidth approached similar values at later times of plasma evolution regardless of the laser energy. The linewidths of the 2Hα transition showed insignificant differences between spatially resolved and spatially integrated measurements.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Rare earth element transport in the western North Atlantic inferred from Nd isotopic observations

The relationship between the Nd isotopic composition in the Atlantic waters and the origin and circulation of the water masses was investigated. Samples were collected in the western North Atlantic between 7 and 54 deg N. The isotopic composition (Nd-143/Nd-144 ratios) showed extensive vertical structure at all locations. In regions where a thermocline was well-developed, large isotopic shifts were observed across the base of the thermocline, while regions without a thermocline were characterized by much more gradual shifts in isotopic composition with depth. The data reveal an excellent correlation between the Nd isotopic distribution in the western North Atlantic water column and the distribution of water masses identified from temperature and salinity measurements.

Piepgras, D. J.↗

Influence of ambient gas on self-reversal in Li transitions relevant to isotopic analysis

Laser induced breakdown spectroscopy is a promising, rapid analysis method for the detection and quantification of Li and its isotopes needed in geochemical, nuclear, and energy storage applications. However, spectral broadening in laser produced plasmas, presence of fine and hyperfine structures, and self-reversal effects make Li isotopic analysis via laser induced breakdown spectroscopy challenging. The present study explores the influence of Ar, N 2 , and He ambient gases over the pressure range of 0.05 - 100 Torr on line broadening and self-reversal of the Li I transition with the greatest isotopic shift in the VIS spectral region (i.e., ≈670.8 nm, ≈15.8 pm isotopic shift). We perform spatially and temporally resolved optical emission spectroscopy of plasmas produced via laser ablation of LiAlO 2 substrates. Our results show that the self-reversal and linewidth is reduced at lower pressures for all gases, and using optimized plasma conditions with chemometric methods, the 6 Li/ 7 Li isotopic ratios can be predicted.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

High-resolution laser system for the S 3 -Low Energy Branch

Here, in this paper we present the first high-resolution laser spectroscopy results obtained at the GISELE laser laboratory of the GANIL-SPIRAL2 facility, in preparation for the first experiments with the S 3 -Low Energy Branch. Studies of neutron-deficient radioactive isotopes of erbium and tin represent the first physics cases to be studied at S 3 . The measured isotope-shift and hyperfine structure data are presented for stable isotopes of these elements. The erbium isotopes were studied using the 4f 12 6s 2 3 H 6 → 4f 12 ( 3 H)6s6p J = 5 atomic transition (415 nm) and the tin isotopes were studied by the 5s 2 5p 2 ( 3 P 0 ) → 5s 2 5p6s( 3 P 1 ) atomic transition (286.4 nm), and are used as a benchmark of the laser setup. Additionally, the tin isotopes were studied by the 5s 2 5p6s( 3 P 1 ) → 5s 2 5p6p( 3 P 2 ) atomic transition (811.6 nm), for which new isotope-shift data was obtained and the corresponding field-shift F 812 and mass-shift M 812 factors are presented.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Isotopic Signatures of Lithium Carbonate and Lithium Hydroxide Monohydrate Measured Using Raman Spectroscopy

Lithium isotopic ratios have wide ranging applications as chemical signatures, including improved understanding of geochemical processes and battery development. Measurement of isotope ratios using optical spectroscopies would provide an alternative to traditional mass spectrometric methods, which are expensive and often limited to a chemical laboratory. In this work, Raman spectra of 7 Li 2 CO 3 , 6 Li 2 CO 3 , 7 LiOH*H 2 O and 6 LiOH*H 2 O have been measured to determine the effect of lithium isotope substitution on the Raman molecular vibrations. Thirteen peaks were observed in the spectrum of lithium carbonate, with discernable isotopic shifts occurring in eleven of the thirteen vibrations, two of which have not been previously reported in the literature. The spectrum of lithium hydroxide monohydrate contained nine peaks, with discernable isotopic shifts occurring in eight of the nine vibrations, four of which have not been previously reported in the literature. The Raman spectral data reported here for lithium carbonate and lithium hydroxide monohydrate are in agreement with the previously reported works in the literature, in which the Raman active modes of these molecules were first identified and assigned. However, due to the stability and resolution of the detection system used in this work, isotopic shifts with a magnitude less than one wavenumber have been identified. Principal Component Regression was used to evaluate the sensitivity to isotopic content of small Raman peak shifts in Li 2 CO 3 and indicates differences greater than 2 atom-% could be reliably determined. These measurements add to the body of work on lithium isotope Raman spectroscopy for these two compounds and increases the number of Raman bands which could be used for lithium isotope content analysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Characterization and Optimization of a Spectral Window for Direct Gaseous Uranium Hexafluoride Enrichment Assay Using Laser-Induced Breakdown Spectroscopy

Through a systematic scanning of 235 U and 238 U emission lines between 280 nm and 745 nm, the optimal emission line for direct gaseous uranium hexafluoride (UF 6 ) enrichment assay using laser-induced breakdown spectroscopy (LIBS) was found. Screening for spectral features that are potentially useful for U isotopic analysis was gauged from the magnitude of the 235 U– 238 U isotopic shift and the signal-to-background ratio of the emission line through a parameter termed ΔSBR 235U–238U . The ΔSBR spectrum shows peaks at wavelength positions where there are strong lines with significant 235 U– 238 U shifts. The screening identified 13 spectral-window candidates, which were down selected based on their overall accuracy in predicting the 235 U enrichment of three UF 6 samples of natural (0.720 atom% 235 U) and low-enriched (4.675 atom% and 9.157 atom% 235 U) grades. The U(I) 646.498 nm emission line, with a determined 235 U– 238 U isotopic shift of -17.7 pm, was found to be the optimal spectral window for direct UF 6 enrichment assay. The root mean square error for enrichment assays on the three natural and low-enriched UF 6 samples, with each sample measured in six replicates, was 0.31% in absolute 235 U content. Each measurement comprised LIBS signals accumulated from 3000 laser shots. In conclusion, the analytical bias and precision were better than 0.5% and 0.3%, respectively, in absolute [ 235 U/( 235 U + 238 U)] ratios. Specific for the two low-enriched UF 6 samples, the relative standard deviations from six replicated measurements were around 2%.

47 OTHER INSTRUMENTATION↗

Evidence of Two-Source King Plot Nonlinearity in Spectroscopic Search for New Boson

Optical precision spectroscopy of isotope shifts can be used to test for new forces beyond the standard model, and to determine basic properties of atomic nuclei. We measure isotope shifts on the highly forbidden 2 S 1/2 → 2 F 7/2 octupole transition of trapped 168,170, 172, 174, 176 Yb ions. When combined with previous measurements in Yb + and very recent measurements in Yb, the data reveal a King plot nonlinearity of up to 240σ. Furthermore, the trends exhibited by experimental data are explained by nuclear density functional theory calculations with the Fayans functional. We also find, with 4.3σ confidence, that there is a second distinct source of nonlinearity, and discuss its possible origin.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Enhancing Molecular Isotope Detection with a Chirp Tuned Optical Centrifuge

This paper gives a brief experimental overview on creating a chirp-tunable optical centrifuge with the goal of amplifying the isotope shift of a given molecule. Results for this experiment were recorded with a CO 2 plume as the probed material. Beyond amplification of the isotope shift, this technology could be modified to alter magnetic field characteristics of common molecules as well as simulating high temperature gases found in combustion environments. Our specific design uses double mirror and grating stretcher and will include a unique tuning feature for customization of the beam’s red and blue components' temporal chirp, allowing for quick reactivity to varying task requirements. The design and parameters will be discussed, as well as the methods used to model the optical centrifuge. Although this experiment is ongoing, results have been gathered previously that display the efficacy of the optical centrifuge. For the probed CO 2 sample, Raman Shifts centered around a wavenumber of 60 and 275 were recorded with durations of 1000 and 800 picoseconds, respectively.

47 OTHER INSTRUMENTATION↗

Configuration–Interaction Perturbation Theory Calculations of Pu II

Configuration–interaction perturbation theory (CI–PT) is applied to calculations of low-energy states of Pu II. This ion is quite challenging due to a large number of possible determinants arising from seven valence electrons and strong relativistic effects. The CI–PT calculations agree with experiments for the energies and g-factors for many low-energy states that allowed positive identification of the theoretical levels. Isotope shifts were also used to aid in identification, and, in case of the odd states, fitting with three independent parameters was used to match theoretical isotope shifts to the experimental values with good accuracy. The CI–PT approach tested here on the Pu II ion can be generally used to calculate properties of many complex atoms, including U I that can find application in fundamental and applied science.

74 ATOMIC AND MOLECULAR PHYSICS↗

Oxygen isotope evidence for input of magmatic fluids and precipitation of Au-Ag-tellurides in an otherwise ordinary adularia-sericite epithermal system in NE China

Abstract Tellurium-rich (Te) adularia-sericite epithermal Au-Ag deposits are an important current and future source of precious and critical metals. However, the source and evolution of ore-forming fluids in these deposits are masked by traditional bulk analysis of quartz oxygen isotope ratios that homogenize fine-scale textures and growth zones. To advance understanding of the source of Te and precious metals, herein, we use petrographic and cathodoluminescence (CL) images of such textures and growth zones to guide high spatial resolution secondary ion mass spectroscopy (SIMS) oxygen isotope analyses (10 µm spot) and spatially correlated fluid inclusion microthermometric measurements on successive quartz bands in contemporary Te-rich and Te-poor adularia-sericite (-quartz) epithermal Au-Ag vein deposits in northeastern China. The results show that large positive oxygen isotope shifts from –7.1 to +7.7‰ in quartz rims are followed by precipitation of Au-Ag telluride minerals in the Te-rich deposit, whereas small oxygen isotope shifts of only 4‰ (–2.2 to +1.6‰) were detected in quartz associated with Au-Ag minerals in the Te-poor deposits. Moreover, fluid-inclusion homogenization temperatures are higher in comb quartz rims (avg. 266.4 to 277.5 °C) followed by Au-Ag telluride minerals than in previous stages (~250 °C) in the Te-rich deposit. The Te-poor deposit has a consistent temperature (~245 °C) in quartz that pre- and postdates Au-Ag minerals. Together, the coupled increase in oxygen isotope ratios and homogenization temperatures followed by precipitation of Au-Ag tellurides strongly supports that inputs of magmatic fluid containing Au, Ag, and Te into barren meteoric water-dominated flow systems are critical to the formation of Te-rich adularia-sericite epithermal Au-Ag deposits. In contrast, Te-poor adularia-sericite epithermal Au-Ag deposits show little or no oxygen isotope or fluid-inclusion evidence for inputs of magmatic fluid.

Geochemistry & Geophysics↗

Nuclear charge densities in spherical and deformed nuclei: Toward precise calculations of charge radii

Precise measurements of atomic transitions affected by electron-nucleus hyperfine interactions offer sensitivity to explore basic properties of the atomic nucleus and study fundamental symmetries, including the search for new physics beyond the standard model of particle physics. Specifically, such measurements, augmented by atomic and nuclear calculations, will enable extraction of the higher-order radial moments of the charge-density distribution in spherical and deformed nuclei. The new data impose higher precision requirements on a theoretical description. The nuclear charge density is composed of the proton point distribution folded with the nucleonic charge distributions. The latter induce subtle relativistic corrections due to the coupling of nucleon magnetic moments with the nuclear spin-orbit density. Additional corrections come from the effect of center-of-mass projection. We assess the precision of nuclear charge density calculations by studying the behavior of relativistic and center-of-mass motion corrections to the second and fourth charge radial moments. Special attention has been paid to the magnetic spin-orbit density associated with the local variations of the spin-orbit current. The calculations for semimagic and open-shell nuclei are performed in the framework of self-consistent mean-field theory using quantified energy density functionals and density-dependent pairing forces. We used the general expression for the spin-orbit form factor that is valid for spherical and deformed nuclei. We studied the impact of various correction terms on the charge radii, fourth radial moments, diffraction radii, and surface thickness of spherical and deformed nuclei. The spin-orbit corrections to charge radial moments and surface thickness show strong shell fluctuations which can make an appreciable effect when aiming at high-precision predictions of isotopic shifts. The inclusion of relativistic and center-of-mass corrections impacts the quality of energy density functionals optimized to charge radii data. To establish reliable constraints on the existence of new forces from isotope shift measurements, precise calculations of nuclear charge densities of deformed nuclei are needed. The proper inclusion of the spin-orbit charge density and other correction terms is essential when aiming at extraction of subtle effects which become particularly visible in isotopic trends. It is also important when developing high-quality nuclear energy density functionals optimized using heterogeneous datasets involving absolute charge radii, differential charge radii, and charge form factor properties deduced from electron-scattering data.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Laser spectroscopy of indium Rydberg atom bunches by electric field ionization

This work reports on the application of a novel electric field-ionization setup for high-resolution laser spectroscopy measurements on bunched fast atomic beams in a collinear geometry. In combination with multi-step resonant excitation to Rydberg states using pulsed lasers, the field ionization technique demonstrates increased sensitivity for isotope separation and measurement of atomic parameters over previous non-resonant laser ionization methods. The setup was tested at the Collinear Resonance Ionization Spectroscopy experiment at ISOLDE-CERN to perform high-resolution measurements of transitions in the indium atom from the 5s 2 5d 2 D 5/2 and 5s 2 5d 2 D 3/2 states to 5s 2 np 2 P and 5s 2 nf 2 F Rydberg states, up to a principal quantum number of n=72 . The extracted Rydberg level energies were used to re-evaluate the ionization potential of the indium atom to be 46,670.107(4)cm -1 . The nuclear magnetic dipole and nuclear electric quadrupole hyperfine structure constants and level isotope shifts of the 5s 2 5d 2 D 5/2 and 5s 2 5d 2 D 3/2 states were determined for 113,115 In. The results are compared to calculations using relativistic coupled-cluster theory. A good agreement is found with the ionization potential and isotope shifts, while disagreement of hyperfine structure constants indicates an increased importance of electron correlations in these excited atomic states. With the aim of further increasing the detection sensitivity for measurements on exotic isotopes, a systematic study of the field-ionization arrangement implemented in the work was performed at the same time and an improved design was simulated and is presented. The improved design offers increased background suppression independent of the distance from field ionization to ion detection.

74 ATOMIC AND MOLECULAR PHYSICS↗

Real-Time Elemental and Isotopic Measurements of Molten Salt Systems through Laser-Induced Breakdown Spectroscopy

Molten salt reactors are an emerging advanced nuclear reactor concept in which the fuel is dissolved into the working fluid in the form of a high-temperature molten salt. The complex, mobile, and corrosive nature of this fluid presents a fundamental challenge for analytical measurements. Tracking species throughout the reactor is important for ensuring proper operation. This article presents laser-induced breakdown spectroscopy (LIBS) used to monitor the elemental composition of a molten salt and corresponding hydrogen isotopic shifts in real-time. A NaNO 3 –KNO 3 eutectic salt was saturated with protium and deuterium gases, then the effluent aerosol stream formed using an argon sparging vessel was monitored with LIBS. This modular LIBS system permitted several spectrometers to be used simultaneously to capture high-resolution isotopic shifts and provide broadband elemental coverage. Further, the results exhibit how LIBS can be used to understand salt–gas chemical and physical interactions such as diffusion. Furthermore, LIBS’ broad elemental coverage can provide greater insight into the chemical reactions within the salt vessel such as the formation of water vapor by monitoring hydrogen and oxygen signatures simultaneously. Ultimately, this study demonstrates the analytical possibilities of LIBS for real-time monitoring of isotopes and elemental composition in molten salt systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗