Nonlinear measurements of kinetics and generalized dynamical modes. II. Application to a simulation of solvation dynamics in an ionic liquid

Solvation dynamics in ionic liquids show features that are often associated with supercooled liquids, including stretched nonexponential relaxation. To better understand the mechanism behind the stretching, the nonlinear mode-correlation methods proposed in Paper I [S. R. Hodge and M. A. Berg, J. Chem. Phys. 155, 024122 (2021)] are applied to a simulation of a prototypical ionic liquid. A full Green's function is recovered. In addition, specific tests for non-Gaussian dynamics are made. No deviations from Gaussian dynamics are found. This finding is incompatible with rate heterogeneity as a cause of the nonexponential relaxation and appears to be in conflict with an earlier multidimensional analysis of the same data. Although this conflict is not resolved here, this work does demonstrate the practicality of mode-correlation analysis in the face of finite datasets and calculations.

Automated summary

This study investigates the solvation dynamics in ionic liquids and finds that the stretched nonexponential relaxation is not caused by rate heterogeneity, which conflicts with an earlier multidimensional analysis of the same data. However, the practicality of mode-correlation analysis in the face of finite datasets and calculations is demonstrated.