The solvent shell structure of aqueous iodide: X-ray absorption spectroscopy and classical, hybrid QM/MM and full quantum molecular dynamics simulations

V. T. Pham, I. Tavernelli, C. J. Milne, R. M. van der Veen, P. D'Angelo, Ch Bressler, M. Chergui

Research output: Contribution to journalArticlepeer-review

Abstract

The L3 X-ray absorption spectrum of aqueous iodide is reported, and its EXAFS is compared to theoretical spectra reconstructed from the radial distribution function of the iodide hydration obtained from classical, hybrid Quantum Mechanics Molecular Mechanics, (QM/MM) and full quantum (density functional theory, DFT) molecular dynamics simulations. Since EXAFS is mainly sensitive to short distances around the iodide ion, it is a direct probe of the local solvation structure. The comparison shows that QM/MM simulations deliver a satisfactory description of the EXAFS signal, while nonpolarizable classical simulations are somewhat less satisfactory and DFT-based simulations perform poorly. We also identify a weak anisotropy of the water solvation shell around iodide, which may be of importance in electron photoejection experiments.

Original languageEnglish (US)
Pages (from-to)24-29
Number of pages6
JournalChemical Physics
Volume371
Issue number1-3
DOIs
StatePublished - May 25 2010

Keywords

  • Aqueous halides
  • DFT
  • EXAFS
  • Molecular dynamics
  • QM/MM
  • Solvation shell
  • X-ray absorption spectroscopy

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

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