title: Rate and Amplitude Heterogeneity in the Solvation Response of an Ionic Liquid.
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.
authors.affiliation: Department of Chemistry and Biochemistry, University of South Carolina , Columbia, South Carolina 29208, United States.
authors.forename: Sachin Dev
authors.initials: SD
authors.lastname: Verma
authors.affiliation: Department of Chemistry and Biochemistry, University of Notre Dame , Notre Dame, Indiana 46556, United States.
authors.forename: Steven A
authors.initials: SA
authors.lastname: Corcelli
authors.affiliation: Department of Chemistry and Biochemistry, University of South Carolina , Columbia, South Carolina 29208, United States.
authors.forename: Mark A
authors.initials: MA
authors.lastname: Berg