Ion-pairing in aqueous CaCl2 and RbBr solutions: Simultaneous structural refinement of XAFS and XRD data

Research output: Contribution to journalArticle


We present a new methodology involving the simultaneous refinement of both x-ray absorption and x-ray diffraction spectra (x-ray absorption/diffraction structural refinement, XADSR) to study the hydration and ion pair structure of CaCl2 and RbBr salts in concentrated aqueous solutions. The XADSR method combines the x-ray absorption fine structure (XAFS) spectral analysis of both the cation and anion as a probe of their short-range structure with an x-ray diffraction (XRD) spectral analysis as a probe of the global structural. Together they deliver a comprehensive picture of the cation and anion hydration, the contact ion pair (CIP) structure, and the solvent-separated ion pair (SSIP) structure. XADSR analysis of 6.0 m aqueous CaCl2 reveals that there are ∼0.26 Ca2+-Cl- CIP's separated by about 2.71 Å, while there are 3.4 SSIP's separated by about 4.98 Å. In contrast XADSR analysis of 6 m aqueous RbBr yields about 0.7 pair CIP at a bond length of 3.51 Å. The present work demonstrates a new approach for a direct co-refinement of XRD and XAFS spectra in a simple and reliable fashion, opening new opportunities for analysis in various disordered and crystalline systems.


  • Van-Thai Pham
  • John L. Fulton
External organisations
  • Pacific Northwest National Laboratory
Original languageEnglish
Article number044201
JournalJournal of Chemical Physics
Issue number4
Publication statusPublished - 2013 Jan 28
Publication categoryResearch
Externally publishedYes