4.8 Article

Rate and Amplitude Heterogeneity in the Solvation Response of an Ionic Liquid

Journal

JOURNAL OF PHYSICAL CHEMISTRY LETTERS
Volume 7, Issue 3, Pages 504-508

Publisher

AMER CHEMICAL SOC
DOI: 10.1021/acs.jpclett.5b02835

Keywords

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Funding

  1. National Science Foundation [CHE-1111530, CHE-1403027]
  2. American Chemical Society Petroleum Research Fund [52648-ND6]
  3. Division Of Chemistry
  4. Direct For Mathematical & Physical Scien [1403027] Funding Source: National Science Foundation

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In contrast with conventional liquids, ionic liquids have solvation dynamics with more rate dispersion and with average times that do not agree with dielectric measurements. A kinetic analog of multidimensional spectroscopy is introduced and used to look for heterogeneity in simulations of coumarin 153 in [Im(12)][BF4]. Strong heterogeneity is found in the diffusive solvation rate. An unanticipated heterogeneity in the amplitude of the inertial solvation is also seen. Both heterogeneities exchange at the same rate. This rate is similar to the mean diffusive solvation time, putting it in the intermediate exchange region. Overall, there are multiple violations of the assumptions usually invoked in the theory of reaction dynamics.

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