Heterogeneous reaction rates in an ionic liquid: quantitative results from two-dimensional multiple population-period transient spectroscopy

The hypotheses that ionic liquids are structurally heterogeneous at the molecular level and, even further, that this heterogeneity can transfer to the rates of reactions run in ionic liquids is being actively debated. Here, this hypothesis is tested using multiple population-period transient spectroscopy (MUPPETS), an emerging type of multidimensional measurement that resolves the kinetics of subensembles within a heterogeneous sample. A previous MUPPETS study of the excited-state twisting and electronic relaxation of auramine indicated that an ionic-liquid solvent induces rate dispersion due to a combination of heterogeneous and homogeneous processes, but those data could not quantitatively separate these contributions [Khurmi, C.; Berg, M. A. J. Phys. Chem. Lett.2010, 1, 161]. New MUPPETS data that include phase resolution and subtraction of thermal gratings are presented here and are successfully modeled. The total range of reaction rates (10--90%) is a factor of 70. If the solvent effect is viewed as a set of local viscosities, the viscosity distribution is broad and highly asymmetric. However, if the solvent is viewed as changing a reaction barrier, the data correspond to a Gaussian distribution of barrier heights. The relaxation of each subensemble is nonexponential with an initial induction period, but the shape of the decay is invariant across the rate distribution. A small (2%), long-lived component is identified as a part of the homogeneous kinetic scheme and thus as a secondary channel for excited-state relaxation, not as an impurity or alternative ground-state form of auramine. On the basis of these results, we suggest that the primary cause of rate heterogeneity is a long-lived local electric field acting on the charge redistribution during the reaction.