The collision cross sections of iodide salt cluster ions in air via differential mobility analysis-mass spectrometry

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

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55 Scopus citations

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. [Figure not available: see fulltext.]

Original languageEnglish (US)
Pages (from-to)1833-1847
Number of pages15
JournalJournal of the American Society for Mass Spectrometry
Volume24
Issue number12
DOIs
StatePublished - Dec 2013

Keywords

  • Cluster ion
  • Collision cross section
  • Differential mobility analysis
  • Gas molecule
  • Ion induced dipole potential
  • Ion mobility
  • Scattering

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