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Title: Rate equation model of laser induced bias in uranium isotope ratios measured by resonance ionization mass spectrometry

Abstract

Resonance Ionization Mass Spectrometry (RIMS) has been developed as a method to measure uranium isotope abundances. In this approach, RIMS is used as an element-selective ionization process between uranium atoms and potential isobars without the aid of chemical purification and separation. The use of broad bandwidth lasers with automated feedback control of wavelength was applied to the measurement of the 235U/238U ratio to decrease laser-induced isotopic fractionation. In application, isotope standards are used to identify and correct bias in measured isotope ratios, but understanding laser-induced bias from first-principles can improve the precision and accuracy of experimental measurements. A rate equation model for predicting the relative ionization probability has been developed to study the effect of variations in laser parameters on the measured isotope ratio. The model uses atomic data and empirical descriptions of laser performance to estimate the laser-induced bias expected in experimental measurements of the 235U/238U ratio. Empirical corrections are also included to account for ionization processes that are difficult to calculate from first principles with the available atomic data. As a result, development of this model has highlighted several important considerations for properly interpreting experimental results.

Authors:
 [1];  [2];  [3];  [4];  [1];  [1]
+ Show Author Affiliations
  1. Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
  2. Univ. of California, Berkeley, CA (United States)
  3. Argonne National Lab. (ANL), Argonne, IL (United States)
  4. Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Publication Date:
Research Org.:
Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1305890
Report Number(s):
LLNL-JRNL-648449
Journal ID: ISSN 0267-9477; JASPE2
Grant/Contract Number:  
AC52-07NA27344
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Analytical Atomic Spectrometry
Additional Journal Information:
Journal Volume: 31; Journal Issue: 3; Journal ID: ISSN 0267-9477
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
74 ATOMIC AND MOLECULAR PHYSICS; 22 GENERAL STUDIES OF NUCLEAR REACTORS

Citation Formats

Isselhardt, B. H., Prussin, S. G., Savina, M. R., Willingham, D. G., Knight, K. B., and Hutcheon, I. D. Rate equation model of laser induced bias in uranium isotope ratios measured by resonance ionization mass spectrometry. United States: N. p., 2015. Web. doi:10.1039/C5JA00249D.
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Isselhardt, B. H., Prussin, S. G., Savina, M. R., Willingham, D. G., Knight, K. B., & Hutcheon, I. D. Rate equation model of laser induced bias in uranium isotope ratios measured by resonance ionization mass spectrometry. United States. https://doi.org/10.1039/C5JA00249D
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Isselhardt, B. H., Prussin, S. G., Savina, M. R., Willingham, D. G., Knight, K. B., and Hutcheon, I. D. Mon . "Rate equation model of laser induced bias in uranium isotope ratios measured by resonance ionization mass spectrometry". United States. https://doi.org/10.1039/C5JA00249D. https://www.osti.gov/servlets/purl/1305890.
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@article{osti_1305890,
title = {Rate equation model of laser induced bias in uranium isotope ratios measured by resonance ionization mass spectrometry},
author = {Isselhardt, B. H. and Prussin, S. G. and Savina, M. R. and Willingham, D. G. and Knight, K. B. and Hutcheon, I. D.},
abstractNote = {Resonance Ionization Mass Spectrometry (RIMS) has been developed as a method to measure uranium isotope abundances. In this approach, RIMS is used as an element-selective ionization process between uranium atoms and potential isobars without the aid of chemical purification and separation. The use of broad bandwidth lasers with automated feedback control of wavelength was applied to the measurement of the 235U/238U ratio to decrease laser-induced isotopic fractionation. In application, isotope standards are used to identify and correct bias in measured isotope ratios, but understanding laser-induced bias from first-principles can improve the precision and accuracy of experimental measurements. A rate equation model for predicting the relative ionization probability has been developed to study the effect of variations in laser parameters on the measured isotope ratio. The model uses atomic data and empirical descriptions of laser performance to estimate the laser-induced bias expected in experimental measurements of the 235U/238U ratio. Empirical corrections are also included to account for ionization processes that are difficult to calculate from first principles with the available atomic data. As a result, development of this model has highlighted several important considerations for properly interpreting experimental results.},
doi = {10.1039/C5JA00249D},
journal = {Journal of Analytical Atomic Spectrometry},
number = 3,
volume = 31,
place = {United States},
year = {Mon Dec 07 00:00:00 EST 2015},
month = {Mon Dec 07 00:00:00 EST 2015}
}
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https://doi.org/10.1039/C5JA00249D
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Works referenced in this record:

Handbook of Basic Atomic Spectroscopic Data
journal, December 2005

  • Sansonetti, J. E.; Martin, W. C.
  • Journal of Physical and Chemical Reference Data, Vol. 34, Issue 4
  • DOI: 10.1063/1.1800011

Isotope fractionation in secondary ion mass spectrometry
journal, March 1982

  • Shimizu, N.; Hart, S. R.
  • Journal of Applied Physics, Vol. 53, Issue 3
  • DOI: 10.1063/1.330636

Effect of hyperfine structure on ionization efficiencies in stepwise ionization using broad bandwidth lasers
journal, January 1991

  • Payne, M. G.; Allman, S. L.; Parks, J. E.
  • Spectrochimica Acta Part B: Atomic Spectroscopy, Vol. 46, Issue 11
  • DOI: 10.1016/0584-8547(91)80197-B

Multi-element isotopic analysis of single presolar SiC grains
journal, October 2006

The Physics of Laser-Atom Interactions
journal, January 1997

Effects of hyperfine structure on coherent excitation
journal, April 1981

Laser spectroscopy of U i using stepwise excitation and fluorescence detection
journal, January 1979

  • Miron, E.; David, R.; Erez, G.
  • Journal of the Optical Society of America, Vol. 69, Issue 2
  • DOI: 10.1364/JOSA.69.000256

Recent developments in isotope ratio measurements by resonance ionization mass spectrometry
journal, April 2005

  • Wendt, Klaus; Trautmann, Norbert
  • International Journal of Mass Spectrometry, Vol. 242, Issue 2-3, p. 161-168
  • DOI: 10.1016/j.ijms.2004.11.008

Optimization of the conditions for simultaneous non-selective excitation of plutonium isotopes for isotope ratio measurements in resonance ionization mass spectrometry
journal, July 2006

  • Sankari, M.; Kumar, P. V. Kiran; Suryanarayana, M. V.
  • International Journal of Mass Spectrometry, Vol. 254, Issue 1-2
  • DOI: 10.1016/j.ijms.2006.05.019

High-precision measurement of ^235U ground-state hyperfine structure by laser-rf double resonance
journal, January 1979

  • Childs, W. J.; Poulsen, O.; Goodman, L. S.
  • Optics Letters, Vol. 4, Issue 1
  • DOI: 10.1364/OL.4.000035

Surface Analysis by SNMS: Femtosecond Laser Postionization of Sputtered and Laser Desorbed Atoms
journal, June 1996

Velocity distribution of sputtered U atoms as determined by laser induced fluorescence spectroscopy
journal, April 1981

Applications of resonance ionization mass spectrometry
journal, August 1994

  • Payne, M. G.; Deng, Lu; Thonnard, N.
  • Review of Scientific Instruments, Vol. 65, Issue 8
  • DOI: 10.1063/1.1144702

Resonance ionization mass spectrometry for precise measurements of isotope ratios
journal, November 2009

  • Levine, Jonathan; Savina, Michael R.; Stephan, Thomas
  • International Journal of Mass Spectrometry, Vol. 288, Issue 1-3
  • DOI: 10.1016/j.ijms.2009.07.013

Effects of magnetic sublevel degeneracy on Rabi oscillations
journal, May 1978

New spectroscopic data on high-lying excited levels of atomic uranium
journal, January 1982

  • Coste, A.; Avril, R.; Blancard, P.
  • Journal of the Optical Society of America, Vol. 72, Issue 1
  • DOI: 10.1364/JOSA.72.000103

Analyzing individual presolar grains with CHARISMA
journal, September 2003

High-resolution triple-resonance autoionization of uranium isotopes
journal, November 2005

  • Schumann, P. G.; Wendt, K. D. A.; Bushaw, B. A.
  • Spectrochimica Acta Part B: Atomic Spectroscopy, Vol. 60, Issue 11
  • DOI: 10.1016/j.sab.2005.08.010

Theory of resonant ionization by broad-band radiation in the determination of isotopic abundances
journal, August 1989

Ultratrace Uranium Fingerprinting with Isotope Selective Laser Ionization Spectrometry
journal, August 2008

  • Ziegler, Summer L.; Bushaw, Bruce A.
  • Analytical Chemistry, Vol. 80, Issue 15
  • DOI: 10.1021/ac800764j

Systematics of isotope ratio measurements with resonant laser photoionization sources
conference, May 1992

  • Wunderlich, Rainer K.; Hutcheon, Ian D.; Wasserburg, G. J.
  • OE/LASE '92, SPIE Proceedings
  • DOI: 10.1117/12.59314

Highly excited odd-parity levels of atomic uranium
journal, October 2000

  • Miyabe, Masabumi; Oba, Masaki; Wakaida, Ikuo
  • Journal of Physics B: Atomic, Molecular and Optical Physics, Vol. 33, Issue 21
  • DOI: 10.1088/0953-4075/33/21/333

Rate equations versus Bloch equations in multiphoton ionization
journal, July 1977

New instrument for microbeam analysis incorporating submicron imaging and resonance ionization mass spectrometry
journal, May 1995

  • Ma, Z.; Thompson, R. N.; Lykke, K. R.
  • Review of Scientific Instruments, Vol. 66, Issue 5
  • DOI: 10.1063/1.1145546

Statistical broadening and population loss in strongly excited three-level systems
journal, January 1979

Improving Precision in Resonance Ionization Mass Spectrometry: Influence of Laser Bandwidth in Uranium Isotope Ratio Measurements
journal, April 2011

  • Isselhardt, B. H.; Savina, M. R.; Knight, K. B.
  • Analytical Chemistry, Vol. 83, Issue 7
  • DOI: 10.1021/ac102586v

Isotope Ratio Biases in Resonance Ionization Mass Spectroscopy Due to Population Trapping
journal, August 1990

Conditions for population trapping in a three-level system
journal, October 1982

Improved isotopic SIMS measurements of uranium particles for nuclear safeguard purposes
journal, January 2009

  • Ranebo, Y.; Hedberg, P. M. L.; Whitehouse, M. J.
  • Journal of Analytical Atomic Spectrometry, Vol. 24, Issue 3
  • DOI: 10.1039/b810474c

Identification of new high-lying odd energy levels of uranium by resonance ionization mass spectrometry
journal, December 1991

  • Smyth, M. H. C.; Green, L. W.; Sopchyshyn, F. C.
  • Journal of Physics B: Atomic, Molecular and Optical Physics, Vol. 24, Issue 23
  • DOI: 10.1088/0953-4075/24/23/017

Theory of doubly resonant ionization by broad-band radiation applied to the determination of isotopic abundances
journal, July 1990

Laser-induced isotopic effects in titanium resonance ionization
journal, May 1993

  • Wunderlich, R. K.; Wasserburg, G. J.; Hutcheon, I. D.
  • Analytical Chemistry, Vol. 65, Issue 10
  • DOI: 10.1021/ac00058a018

Resonance ionization mass spectrometry of ion beam sputtered neutrals for element- and isotope-selective analysis of plutonium in micro-particles
journal, June 2009

  • Erdmann, N.; Kratz, J. -V.; Trautmann, N.
  • Analytical and Bioanalytical Chemistry, Vol. 395, Issue 6
  • DOI: 10.1007/s00216-009-2906-6
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