0000000000033319
AUTHOR
Bruce A. Bushaw
Determination of90Sr in environmental samples with resonance ionization spectroscopy in collinear geometry
A new, fast technique for trace analysis of the radioactive isotopes89Sr and90Sr in environmental samples has been developed. Conventional mass separation is combined with resonance ionization spectroscopy in collinear geometry, which provides high selectivity and sensitivity. In addition, a chemical separation procedure for sample preparation has been developed. The described technique was used to determine the90Sr content in ≈ 870 m3 air samples collected near Munich during and shortly after the Chernobyl reactor accident in April 1986. The content of90Sr was measured to be 1.4 mBq per m3, corresponding to 1.6 × 109 atoms of90Sr per sample. This value is in good agreement with the results…
Lineshapes and optical selectivity in high-resolution double-resonance ionization mass spectrometry
Abstract Lineshapes expected in high-resolution double-resonance ionization spectroscopy are calculated using the density matrix formalism, integrated over experimentally realistic conditions including atomic velocity and angular distributions as well as laser intensity profiles. The results of these calculations are compared with experimental measurements on the system 4s2 1S0 → 4s4p 1P1 → 4s4d 1D1 → ion for calcium. The measurements of lineshape, with a dynamic range of >106, reveal and confirm subtle effects predicted by theory. These include the shape, position and intensity of the laser-induced structure in the spectra and the simultaneous presence of coherent and incoherent excitation…
Laser resonance ionization for efficient and selective ionization of rare species
Abstract Due to the steady development and refinement of powerful pulsed as well as continuous-wave lasers, resonance ionization has developed into an extremely versatile tool for numerous applications. Apart from suppressing isobaric interferences and contributing to isotopic selectivity already in the ionization process, resonant optical excitation and ionization with laser light ensures high overall efficiency and good temporal and spatial controls of the ions delivered to mass spectrometric applications. In the field of rare isotope research laser resonance ionization has nowadays become one of the key techniques, including similarly the determination of long-lived or stable ultra-trace…
High-resolution triple-resonance autoionization of uranium isotopes
Abstract The near-threshold autoionization (AI) spectrum of uranium has been investigated by triple-resonance excitation with single-mode continuous lasers. Spectra were recorded over the first ∼30 cm − 1 above the first ionization limit at a resolution of 3 × 10 − 4 cm − 1 using intermediate states with different J values (6, 7, 8) to assign AI level total angular momentum J AI = 5 to 9. Resonances with widths ranging from 8 MHz to 30 GHz were observed; the strongest ones have J AI = 9 and widths of ∼60 MHz. Hyperfine structures for 235 U and isotope shifts for 234, 235 U have been measured in the two intermediate levels and in the final AI level for the most favorable excitation path. T…
Triple-resonance autoionization of uranium optimized for diode laser excitation
Abstract The photoionization of uranium via three-step excitation has been optimized for isotope selective trace analysis. A search found 13 new J = 6, 7, and 8 odd-parity states in the 36,850–37,200 cm− 1 region that allow blue–red–red three-photon excitation at wavelengths favorable for commercial diode laser systems. From each of these 13 states, near-threshold autoionization spectra were recorded at a resolution of 3 × 10− 4 cm− 1. Some 30 even-parity autoionizing levels with J = 5 to 9 have also been observed and characterized. Comparison of the spectra allows J assignment for the new intermediate levels as well as selection of an optimized path for trace analysis. We show that, for a …
Determination of the154Sm ionization energy by high-precision laser spectroscopy
High-resolution resonance ionization mass spectrometry has been used to determine the ionization energy of 154Sm. Three-step resonant excitation with single-frequency lasers populates a series of ? = 3, J = 4 Rydberg levels in the range of n = 60?160, covering the range of 30 cm?1 to 4 cm?1 below the first ionization limit. Although samarium has a complex electronic structure with eight valence electrons, series of nearly unperturbed levels could be observed. Analysis includes shifts caused by a single perturbing state, an extended Ritz term for quantum defect variation at lower n, and corrections for residual electric fields. The resulting series convergence limit has an uncertainty of 4 ?…
Trace Analysis of the Radionuclides90Sr and89Sr in Environmental Samples I: Laser Mass Spectrometry
Isotope shifts and hyperfine structure in calcium 4snp and 4snf F Rydberg states
Isotope shifts and hyperfine structure have been measured in 4snp 1 P1 and Rydberg states for all stable calcium isotopes and the radioisotope 41Ca using high-resolution laser spectroscopy. Triple-resonance excitation via Rydberg state was followed by photoionization with a CO2 laser and mass selective ion detection. Isotope shifts for the even-mass isotopes have been analyzed to derive specific mass shift and field shift factors. The apparent isotope shifts for 41Ca and 43Ca exhibit anomalous values that are n-dependent. This is interpreted in terms of hyperfine-induced fine-structure mixing, which becomes very pronounced when singlet-triplet fine-structure splitting is comparable to the h…
Peak shape for a quadrupole mass spectrometer: comparison of computer simulation and experiment
Abstract Computer simulations of ion trajectories have been used to evaluate the performance of a quadrupole mass spectrometer. Consideration has been given to realistic fields modeled on a commercial system as well as experimental distributions with respect to ion entry position, axial and radial velocity and relative phase of the quadrupole field. Determination of the mass filter acceptance-area as a function of the mass setting yields mass peak shapes with a dynamic range of more than seven orders of magnitude and thus provides estimates for abundance sensitivity. Results from these simulations are found to give excellent agreement with experimental measurements for different elements in…
Isotope-shift measurements of stable and short-lived lithium isotopes for nuclear-charge-radii determination
Changes in the mean-square nuclear charge radii along the lithium isotopic chain were determined using a combination of precise isotope shift measurements and theoretical atomic structure calculations. Nuclear charge radii of light elements are of high interest due to the appearance of the nuclear halo phenomenon in this region of the nuclear chart. During the past years we have developed a new laser spectroscopic approach to determine the charge radii of lithium isotopes which combines high sensitivity, speed, and accuracy to measure the extremely small field shift of an 8 ms lifetime isotope with production rates on the order of only 10,000 atoms/s. The method was applied to all bound iso…
Absolute frequency measurements on the 2S→3S transition of lithium-6,7
The frequencies of the 2S–3S two-photon transition for the stable lithium isotopes were measured by cavity-enhanced Doppler-free laser excitation that was controlled by a femtosecond frequency comb. The resulting values of 815 618 181.57(18) and 815 606 727.59(18) MHz, respectively, for 7Li and 6Li are in agreement with previous measurements but are more accurate by an order of magnitude. There is still a discrepancy of about 11.6 and 10.6 MHz from the latest theoretical values. This is comparable to the uncertainty in the theoretical calculations, while uncertainty in our experimental values is more than a hundred-fold smaller. More accurate theoretical calculation of the transition freque…
Spurenbestimmung der Radionuclide90Sr und89Sr in Umweltproben I: Laser-Massenspektrometrie
Isotope shifts and hyperfine structure in the transitions of stable calcium isotopes and calcium-41
Isotope shifts and hyperfine structure in the 4s2 1S0 → 4s4p 1P1 and 4s2 1S0 → 4s4d 1D2 transitions of calcium have been measured with high-precision laser spectroscopy. Calcium atoms in an atomic beam were excited with single-frequency cw dye and titanium sapphire lasers and then photoionized with the 363.8 nm or 514.5 nm line of an argon ion laser. The resulting ions were analyzed and detected with a quadrupole mass spectrometer. Isotope shifts for all stable calcium isotopes and the radionuclide 41Ca have been measured in both transitions. The corresponding field shift and specific mass shift coefficients as well as hyperfine structure constants for the isotopes 41, 43Ca have been derive…
Resonant laser ionization mass spectrometry: An alternative to AMS?
Resonant laser ionization mass spectrometry (RIMS) has developed into a versatile experimental method particularly concerning applications for highly selective ultratrace analysis. Apart from providing nearly complete isobaric suppression and high overall efficiency, the possibility for combining optical isotopic selectivity with that of the mass spectrometer leads to remarkable specifications. The widespread analytical potential and applicability of different techniques based on resonant laser ionization is demonstrated in investigations on stable and radioactive ultratrace isotopes with the focus on applications which require high selectivity, concerning, e.g., the noble gas isotopes 81,8…
Isotope shifts and hyperfine structure in the transitions of gadolinium
High-resolution resonance ionization mass spectrometry has been used to measure isotope shifts and hyperfine structure in all (J = 2-6) and the transitions of gadolinium (Gd I). Gadolinium atoms in an atomic beam were excited with a tunable single-frequency laser in the wavelength range of 422-429 nm. Resonant excitation was followed by photoionization with the 363.8 nm line of an argon ion laser and resulting ions were mass separated and detected with a quadrupole mass spectrometer. Isotope shifts for all stable gadolinium isotopes in these transitions have been measured for the first time. Additionally, the hyperfine structure constants of the upper states have been derived for the isotop…
Double-resonance measurements of isotope shifts and hyperfine structure in Gd I with hyperfine-state selection in an intermediate level
Isotope shifts and hyperfine structure have been measured in the 4f7 5d6s2 9D6 -- X9 D6 (;38 024. 9 cm-1) transition in atomic gadolinium using high- resolution resonance ionization mass spectroscopy. Excitation was performed as a resonance-enhanced two-photon transition with the 4f7 5d6s6p 9F7 state as an intermediate level. Selective population of hyperfine states in the first excitation step allowed assignment of all transitions in the complex hyperfine spectrum of the odd isotopes 155,157Gd and evaluation of the magnetic dipole and electric quadrupole hyperfine structure constants for the X 9D6 state. Measured values for the isotope shifts of all stable Gd isotopes have been used to der…
Ultratrace analysis of calcium with high isotopic selectivity by diodelaser resonance ionisation mass spectrometry
A resonance ionisation mass spectrometer for the ultratrace determination of calcium isotopes is presented. It achieves high overall efficiency, ultra-high isotopic abundance sensitivity of more than 1010 and complete suppression of isobars. The system can be used for isotope ratio studies on stable and long-lived trace isotopes with the final goal of radiodating via 41Ca-determination. For the different applications optical one-, two- or three-step resonance excitation and subsequent ionisation is applied using simple and inexpensive diodelasers. Additional mass analysis is accomplished in a commercial quadrupole mass spectrometer. The experimental set-up and first results on synthetical a…
Properties and performance of a quadrupole mass filter used for resonance ionization mass spectrometry
Abstract The performance of commercial quadrupole mass spectrometers (QMS) with a number of imperfections, as compared to the ideal hyperbolic geometry, has been characterized using the computer simulation program simion 3d version 6.0. The analysis of simulated QMS geometries focuses primarily on modeling of the internal potential, the study of field deviations, and the influence of finite length on performance of the QMS. The computer simulation of ion trajectories in the QMS field yields predictions for optimum working conditions and provides estimates for the resolving power and the maximum isotopic abundance sensitivity. Experimental measurements that confirm these expectations are pre…
Hyperfine structure in 5s 4d 3 D ?5snf transitions of87Sr
The hyperfine spectra of the 5s4d3D1-5s20f, 5s4d3D2-5s23f, and 5s 4d3D3-5s32f transitions of87Sr (I=9/2) have been measured by collinear fast beam laser spectroscopy. The structure in the upper configurations is highly perturbed by fine structure splitting that is of comparable size to the hyperfine interaction energy. These perturbations can be adequately treated with conventional matrix diagonalization methods, using the 5s-electron magnetic dipole interaction terma5s and the unperturbed fine structure splittings as input parameters. Additionally, hyperfine constants for the lower 5s4d3D configurations, including theA- andB-factors and a separation of the individuals- andd-electron contri…
Studies of narrow autoionizing resonances in gadolinium
The autoionization (AI) spectrum of gadolinium between the first and second limits has been investigated by triple-resonance excitation with high-resolution cw lasers. A large number of narrow AI resonances have been observed and assigned total angular momentum J values. The resonances are further divided into members of AI Rydberg series converging to the second limit or other ''interloping'' levels. Fine structure in the Rydberg series has been identified and interpreted in terms of Jc j coupling. A number of detailed studies have been performed on the interloping resonances: These include lifetime determination by lineshape analysis, isotope shifts, hyperfine structure, and photoionizati…
Ionization energy ofLi6,7determined by triple-resonance laser spectroscopy
Rydberg level energies for $^{7}\mathrm{Li}$ were measured using triple-resonance laser excitation, followed by drifted field ionization. In addition to the principal $n\phantom{\rule{0.2em}{0ex}}^{2}P$ series, weak Stark mixing from residual electric fields allowed observation of $n\phantom{\rule{0.2em}{0ex}}^{2}S$ and hydrogenic Stark manifold series at higher $n$. Limit analyses for the series yield the spectroscopic ionization energy ${E}_{I}(^{7}\mathrm{Li})=43\phantom{\rule{0.2em}{0ex}}487.159\phantom{\rule{0.2em}{0ex}}40(18)\phantom{\rule{0.3em}{0ex}}{\mathrm{cm}}^{\ensuremath{-}1}$. The $^{6,7}\mathrm{Li}$ isotope shift (IS) was measured in selected $n\phantom{\rule{0.2em}{0ex}}^{2}…
Recent developments in and applications of resonance ionization mass spectrometry
Resonance Ionization Mass Spectrometry (RIMS) has nowadays reached the status of a routine method for sensitive and selective ultratrace determination of long-lived radioactive isotopes in environmental, biomedical and technical samples. It provides high isobaric suppression, high to ultra-high isotopic selectivity and good overall efficiency. Experimental detection limits are as low as 106 atoms per sample and permit the fast and sensitive determination of ultratrace amounts of radiotoxic contaminations. Experimental arrangements for the detection of different radiotoxic isotopes, e.g. 236–244Pu, 89,90Sr and 99Tc in environmental samples are described, and the application of RIMS to the ul…