Collision cross sections and ion structures: Development of a general calculation method via high-quality ion mobility measurements and theoretical modeling

Jong Wha Lee, Kimberly L. Davidson, Matthew F. Bush, Hugh I. Kim

Research output: Contribution to journalArticle

13 Citations (Scopus)

Abstract

Ion mobility mass spectrometry (IM-MS) has become an important tool for the structural investigation of ions in the gas phase. Accurate theoretical evaluation of ion collision cross sections (CCSs) is essential for the effective application of IM-MS in structural studies. However, current theoretical tools have limitations in accurately describing a broad range of ions from small molecules to macromolecules. Significant difficulties in developing theoretical tools for CCS calculations are associated with obtaining high-quality experimental data and molecular models. In this study, we present a general CCS calculation method by employing two drift-tube IM-MS (DTIM-MS) instruments and thorough molecular modeling procedures. It is demonstrated that an appropriate description of the van der Waals (vdW) interactions is important for accurate CCS calculations in helium drift gas. By utilizing the vdW potentials from molecular mechanics force fields, it is shown that both the appropriate vdW potential-forms and their parameters are necessary for the highly reliable CCS predictions of small molecules. We further show that specific characteristics of the vdW interaction potential become less influential on the calculated CCS with increasing ion size, and that the calculated CCS values for the macromolecules converge to the values at the hard-sphere limit. Based on these results, a general CCS calculation method is presented that can be applied to ions of various sizes and compositions for the gas-phase structural studies.

Original languageEnglish
Pages (from-to)4289-4298
Number of pages10
JournalAnalyst
Volume142
Issue number22
DOIs
Publication statusPublished - 2017 Nov 21

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cross section
collision
Ions
ion
modeling
Mass spectrometry
Mass Spectrometry
mass spectrometry
Gases
Macromolecules
gas
Helium
Molecular mechanics
Molecules
Molecular Models
Molecular modeling
calculation method
Mechanics
helium
mechanics

ASJC Scopus subject areas

  • Analytical Chemistry
  • Biochemistry
  • Environmental Chemistry
  • Spectroscopy
  • Electrochemistry

Cite this

Collision cross sections and ion structures : Development of a general calculation method via high-quality ion mobility measurements and theoretical modeling. / Lee, Jong Wha; Davidson, Kimberly L.; Bush, Matthew F.; Kim, Hugh I.

In: Analyst, Vol. 142, No. 22, 21.11.2017, p. 4289-4298.

Research output: Contribution to journalArticle

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