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Monte Carlo Simulation of Ion Trajectories of Reacting Chemical Systems: Mobility of Small Water Clusters in Ion Mobility Spectrometry

  • Research Article
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Journal of The American Society for Mass Spectrometry

Abstract

For the comprehensive simulation of ion trajectories including reactive collisions at elevated pressure conditions, a chemical reaction simulation (RS) extension to the popular SIMION software package was developed, which is based on the Monte Carlo statistical approach. The RS extension is of particular interest to SIMION users who wish to simulate ion trajectories in collision dominated environments such as atmospheric pressure ion sources, ion guides (e.g., funnels, transfer multi poles), chemical reaction chambers (e.g., proton transfer tubes), and/or ion mobility analyzers. It is well known that ion molecule reaction rate constants frequently reach or exceed the collision limit obtained from kinetic gas theory. Thus with a typical dwell time of ions within the above mentioned devices in the ms range, chemical transformation reactions are likely to occur. In other words, individual ions change critical parameters such as mass, mobility, and chemical reactivity en passage to the analyzer, which naturally strongly affects their trajectories. The RS method simulates elementary reaction events of individual ions reflecting the behavior of a large ensemble by a representative set of simulated reacting particles. The simulation of the proton bound water cluster reactant ion peak (RIP) in ion mobility spectrometry (IMS) was chosen as a benchmark problem. For this purpose, the RIP was experimentally determined as a function of the background water concentration present in the IMS drift tube. It is shown that simulation and experimental data are in very good agreement, demonstrating the validity of the method.

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Notes

  1. The reverse reaction rate constant is calculated as 1.68·10-9 cm3/molecule [8, 9] at p=1 bar (2.4x1019 molecule/cm3), cf. Table 1. The calculated lifetime is the inverse of the pseudo-first order rate constant 1/k = 2x10-11 s or 20 ps.

  2. Er = E/N with E = electrical field strength [V cm-1] and N = molecular number density [molecule cm-3] resulting in the unit V molecule cm-2. More conveniently defined: 1 Td (Townsend) = 10-17 V molecule cm-2.

  3. A detailed derivation of the exact reaction probability is given in the supplemental materials. For sufficiently short time-steps as applied here, the reaction probability is safely approximated by a linear function.

  4. The RS code (including SDS) was made available with SIMION 8.1.1.16. The RS code alone is freely available under the GPL license at http://RS.ipams.uni-wuppertal.de.

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Acknowledgments

The authors are indebted to David Manura (Scientific Instrument Services Inc., Ringoes, USA) for code and documentation review of the RS extension.Footnote 4 Financial support of the German Research Foundation (DFG, project BE BE2124/6-1), the Bundesministerium für Bildung und Forschung, and the Ministerium für Innovation, Wissenschaft und Forschung des Landes Nordrhein-Westfahlen, Germany, is greatly acknowledged. WW acknowledges support through a graduate student research stipend from the Institute of Pure and Applied Mass Spectrometry, University of Wuppertal, Germany. G.A.S. – Gesellschaft für Analytische Sensorsysteme GmbH, Dortmund – kindly provided the technical support for the experimental setup.

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Authors and Affiliations

  1. Institute for Pure and Applied Mass Spectrometry, Physical and Theoretical Chemistry, University of Wuppertal, Wuppertal, Germany

    Walter Wissdorf, Valerie Derpmann, Sonja Klee & Thorsten Benter

  2. Leibnitz-Institut für Analytische Wissenschaften-ISAS-e.V., Dortmund, Germany

    Luzia Seifert & Wolfgang Vautz

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  1. Walter Wissdorf
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  2. Luzia Seifert
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  3. Valerie Derpmann
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  4. Sonja Klee
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  5. Wolfgang Vautz
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  6. Thorsten Benter
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Correspondence to Walter Wissdorf or Thorsten Benter.

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Wissdorf, W., Seifert, L., Derpmann, V. et al. Monte Carlo Simulation of Ion Trajectories of Reacting Chemical Systems: Mobility of Small Water Clusters in Ion Mobility Spectrometry. J. Am. Soc. Mass Spectrom. 24, 632–641 (2013). https://doi.org/10.1007/s13361-012-0553-1

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