Structural investigation of lithium iodide in liquid dimethyl sulfoxide: Comparison between experiment and computation

T. Megyes, I. Bakó, T. Radnái, T. Grósz, Tamás Kosztolányi, Barbara Mroz, Michael Probst

Research output: Contribution to journalArticle

16 Citations (Scopus)

Abstract

We report a combined experimental (X-ray and neutron diffraction) and theoretical (ab initio calculations and molecular dynamics simulation) study of LiI in dimethyl sulfoxide (DMSO) solution. The total structure function computed from MD agrees well with those obtained from both X-ray and neutron diffraction experiments. Evidence was found for Li-I contact ion pair formation in solution. The overall coordination number of Li+ was found to be four, while the Li-DMSO coordination number is below four; the coordination sphere of the I- ion contains eight species (DMSO and lithium) in average and does not show any special geometrical arrangement. Ab initio calculations for clusters containing Li+ and up to six DMSO molecules have been performed with the B3LYP density functional and various basis sets. The calculations show an increase of the average ion-ligand distance from about 1.71-1.96 Å when the number of DMSO molecules in the cluster increases from 1 to 4. The corresponding Li-DMSO interaction energy decreases accordingly; additional DMSO molecules are accommodated in the second shell, in agreement with the results from diffraction experiments and the simulation.

Original languageEnglish
Pages (from-to)100-110
Number of pages11
JournalChemical Physics
Volume321
Issue number1-2
DOIs
Publication statusPublished - Jan 25 2006

Fingerprint

Iodides
Dimethyl Sulfoxide
Lithium
iodides
lithium
coordination number
neutron diffraction
Liquids
liquids
diffraction
molecules
ions
Experiments
Ions
Neutron diffraction
x rays
Molecules
simulation
molecular dynamics
ligands

Keywords

  • DFT
  • DMSO
  • Neutron diffraction
  • Solution
  • X-ray

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Spectroscopy
  • Atomic and Molecular Physics, and Optics

Cite this

Structural investigation of lithium iodide in liquid dimethyl sulfoxide : Comparison between experiment and computation. / Megyes, T.; Bakó, I.; Radnái, T.; Grósz, T.; Kosztolányi, Tamás; Mroz, Barbara; Probst, Michael.

In: Chemical Physics, Vol. 321, No. 1-2, 25.01.2006, p. 100-110.

Research output: Contribution to journalArticle

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AB - We report a combined experimental (X-ray and neutron diffraction) and theoretical (ab initio calculations and molecular dynamics simulation) study of LiI in dimethyl sulfoxide (DMSO) solution. The total structure function computed from MD agrees well with those obtained from both X-ray and neutron diffraction experiments. Evidence was found for Li-I contact ion pair formation in solution. The overall coordination number of Li+ was found to be four, while the Li-DMSO coordination number is below four; the coordination sphere of the I- ion contains eight species (DMSO and lithium) in average and does not show any special geometrical arrangement. Ab initio calculations for clusters containing Li+ and up to six DMSO molecules have been performed with the B3LYP density functional and various basis sets. The calculations show an increase of the average ion-ligand distance from about 1.71-1.96 Å when the number of DMSO molecules in the cluster increases from 1 to 4. The corresponding Li-DMSO interaction energy decreases accordingly; additional DMSO molecules are accommodated in the second shell, in agreement with the results from diffraction experiments and the simulation.

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