Alteration of gas phase ion polarizabilities upon hydration in high dielectric liquids

Sahin Buyukdagli, Tapio Ala-Nissilä

Research output: Contribution to journalArticleScientificpeer-review

14 Citations (Scopus)
69 Downloads (Pure)

Abstract

We investigate the modification of gas phase ion polarizabilities upon solvation in polar solvents and ionic liquids. To this aim, we develop a classical electrostatic theory of charged liquids composed of solvent molecules modeled as finite size dipoles, and embedding polarizable ions that consist of Drude oscillators. In qualitative agreement with ab initio calculations of polar solvents and ionic liquids, the hydration energy of a polarizable ion in both types of dielectric liquid is shown to favor the expansion of its electronic cloud. Namely, the ion carrying no dipole moment in the gas phase acquires a dipole moment in the liquid environment, but its electron cloud also reaches an enhanced rigidity. We find that the overall effect is an increase of the gas phase polarizability upon hydration. In the specific case of ionic liquids, it is shown that this hydration process is driven by a collective solvation mechanism where the dipole moment of a polarizable ion induced by its interaction with surrounding ions self-consistently adds to the polarization of the liquid, thereby amplifying the dielectric permittivity of the medium in a substantial way. We propose this self-consistent hydration as the underlying mechanism behind the high dielectric permittivities of ionic liquids composed of small charges with negligible gas phase dipole moment. Hydration being a correlation effect, the emerging picture indicates that electrostatic correlations cannot be neglected in polarizable liquids.
Original languageEnglish
Article number044907
Pages (from-to)1-11
JournalJournal of Chemical Physics
Volume139
Issue number4
DOIs
Publication statusPublished - 2013
MoE publication typeA1 Journal article-refereed

Keywords

  • ionic liquids
  • polar solvants
  • polarizable ions
  • solvation

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