Impact of anion polarizability on ion pairing in microhydrated salt clusters

Research output: Contribution to journalResearch articleContributedpeer-review

Contributors

  • Arghya Chakraborty - , Leipzig University (Author)
  • Thomas Brumme - , Chair of Theoretical Chemistry, Leipzig University (Author)
  • Sonja Schmahl - , Leipzig University (Author)
  • Hendrik Weiske - , Leipzig University (Author)
  • Carsten Baldauf - , Fritz Haber Institute of the Max Planck Society (Author)
  • Knut R. Asmis - , Leipzig University (Author)

Abstract

Despite longstanding interest in the mechanism of salt dissolution in aqueous media, a molecular level understanding remains incomplete. Here, cryogenic ion trap vibrational action spectroscopy is combined with electronic structure calculations to track salt hydration in a gas phase model system one water molecule at a time. The infrared photodissociation spectra of microhydrated lithium dihalide anions [LiXX′(H2O)n] (XX′ = I2, ClI and Cl2; n = 1-3) in the OH stretching region (3800-2800 cm−1) provide a detailed picture of how anion polarizability influences the competition among ion-ion, ion-water and water-water interactions. While exclusively contact ion pairs are observed for n = 1, the formation of solvent-shared ion pairs, identified by markedly red-shifted OH stretching bands (<3200 cm−1), originating from the bridging water molecules, is favored already for n = 2. For n = 3, Li+ reaches its maximum coordination number of four only in [LiI2(H2O)3], in accordance with the hard and soft Lewis acid and base principle. Water-water hydrogen bond formation leads to a different solvent-shared ion pair motif in [LiI2(H2O)3] and network formation even restabilizes the contact ion pair motif in [LiCl2(H2O)3]. Structural assignments are exclusively possible after the consideration of anharmonic effects. Molecular dynamics simulations confirm that the significance of large amplitude motion (of the water molecules) increases with increasing anion polarizability and that needs to be considered already at cryogenic temperatures.

Details

Original languageEnglish
Pages (from-to)13187-13200
JournalChemical science
Volume109
Issue number8
Publication statusPublished - 16 Nov 2022
Peer-reviewedYes

External IDs

PubMed 36425505

Keywords

ASJC Scopus subject areas