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The Collision Cross Sections of Iodide Salt Cluster Ions in Air via Differential Mobility Analysis-Mass Spectrometry

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Journal of The American Society for Mass Spectrometry

Abstract

To date, most collision cross section (CCS) predictions have invoked gas molecule impingement-reemission rules in which specular and elastic scattering of spherical gas molecules from rigid polyatomic surfaces are assumed. Although such predictions have been shown to agree well with CCSs measured in helium bath gas, a number of studies reveal that these predictions do not agree with CCSs for ions in diatomic gases, namely, air and molecular nitrogen. To further examine the validity of specular-elastic versus diffuse-inelastic scattering models, we measured the CCSs of positively charged metal iodide cluster ions of the form [MI]n[M+]z, where M = Na, K, Rb, or Cs, n = 1 – 25, and z = 1 – 2. Measurements were made in air via differential mobility analysis mass spectrometry (DMA-MS). The CCSs measured are compared with specular-elastic as well as diffuse-inelastic scattering model predictions with candidate ion structures determined from density functional theory. It is found that predictions from diffuse-inelastic collision models agree well (within 5 %) with measurements from sodium iodide cluster ions, while specular-elastic collision model predictions are in better agreement with cesium iodide cluster ion measurements. The agreement with diffuse-inelastic and specular-elastic predictions decreases and increases, respectively, with increasing cation mass. However, even when diffuse-inelastic cluster ion predictions disagree with measurements, the disagreement is of a near-constant factor for all ions, indicating that a simple linear rescaling collapses predictions to measurements. Conversely, rescaling cannot be used to collapse specular-elastic predictions to measurements; hence, although the precise impingement reemission rules remain ambiguous, they are not specular-elastic.

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Acknowledgments

This work was supported by NSF grant CHE-1011810. C.L. acknowledges support from the Ramon Areces Foundation and D.O. acknowledges support from a NSF Graduate Research Fellowship. The authors thank the Minnesota Supercomputing Institute for providing the computational resources needed for density functional theory calculations.

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  1. Department of Mechanical Engineering, University of Minnesota, Minneapolis, MN, 55455, USA

    Hui Ouyang, Carlos Larriba-Andaluz, Derek R. Oberreit & Christopher J. Hogan Jr.

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  1. Hui Ouyang
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  2. Carlos Larriba-Andaluz
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  3. Derek R. Oberreit
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  4. Christopher J. Hogan Jr.
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ESM 1

Table S1, listing experimentally determined collision cross sections, a description of the procedure used to find the “best fit” values of the momentum scattering coefficients, ξ, for KI, RbI, and CsI clusters, and the coordinates and energies of the DFT determined structures in this work are provided. (PDF 1086 kb)

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Ouyang, H., Larriba-Andaluz, C., Oberreit, D.R. et al. The Collision Cross Sections of Iodide Salt Cluster Ions in Air via Differential Mobility Analysis-Mass Spectrometry. J. Am. Soc. Mass Spectrom. 24, 1833–1847 (2013). https://doi.org/10.1007/s13361-013-0724-8

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