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

The Journal of Physical Chemistry Letters
Sachin Dev VermaM Berg

Abstract

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 [Im12][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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Citations

Aug 9, 2016·The Journal of Chemical Physics·Mark A Berg, Jason R Darvin
Oct 27, 2016·The Journal of Chemical Physics·Roger F Loring
Oct 12, 2018·The Journal of Chemical Physics·Jiannan LiuHyung J Kim
Nov 7, 2019·The Journal of Physical Chemistry. B·Sharmistha DasAnindya Datta
Mar 7, 2020·The Journal of Physical Chemistry. B·Sk Saddam HossainAnunay Samanta
Oct 17, 2019·The Journal of Physical Chemistry Letters·Jason R Darvin, Mark A Berg
Oct 29, 2021·The Journal of Physical Chemistry. B·Sharmistha DasAnindya Datta

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