Broadband non‐selective excitation of plutonium isotopes for isotope ratio measurements in resonance ionization mass spectrometry: a theoretical study

RATIONALE Making isotope ratio measurements with minimum isotope bias has always been a challenging task to mass spectrometrists, especially for the specific case of plutonium, owing to the strategic importance of the element. In order to use resonance ionization mass spectrometry (RIMS) as a tool for isotope ratio measurements, optimization of the various laser parameters and other atomic and system parameters is critical to minimize isotopic biases. METHODS Broadband simultaneous non‐selective excitation of the isotopes of plutonium in the triple resonance excitation scheme with λ 1  = 420.77 nm, λ 2  = 847.28 nm, and λ 3  = 767.53 nm based on density matrix formalism has been theoretically computed for the determination of isotope ratios. The effects of the various laser parameters and other factors such as the atomization temperature and the dimensions of the atomic beam on the estimation of isotope ratios were studied. The effects of Doppler broadening, and time‐dependent excitation parameters such as Rabi frequencies, ionization rate and the effect of non‐Lorenztian lineshape have all been incorporated. RESULTS The average laser powers and bandwidths for the three‐excitation steps were evaluated for non‐selective excitation. The laser intensity required to saturate the three‐excitation steps were studied. The two‐dimensional lineshape contour and its features were investigated, while the reversal of peak asymmetry of two‐step and two‐photon excitation peaks under these conditions is discussed. Optimized powers for the non‐selective ionization of the three transitions were calculated as 545 mW, 150 mW and 545 mW and the laser bandwidth for all the three steps was ~20 GHz. CONCLUSIONS The isotopic bias between the resonant and off‐resonant isotope under the optimized conditions was no more than 9%, which is better than an earlier reported value. These optimized laser power and bandwidth conditions are better than in the earlier experimental work since these comprehensive calculations yield simultaneous and much more accurate isotope ratios than those in the sequential and less accurate determination reported earlier. Application of these theoretical calculations to minimize the isotopic biases under these conditions for the rapid, efficient and accurate isotope ratio measurements using RIMS has been outlined. Copyright © 2012 John Wiley & Sons, Ltd.