Dispersed kinetics without rate heterogeneity in an ionic liquid measured with multiple population-period transient spectroscopy
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Berg, Mark
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Abstract
The kinetics of the electronic-state relaxation of the diphenylmethane dye auramine O are found to be much more dispersed (nonexponential) in a prototypical ionic liquid, 1-butyl-3-methylimidazolium hexafluorophosphate, than in ordinary solvents. Recent theoretical and experimental evidence for structural heterogeneity in ionic liquids suggest that the dispersion is due to rate heterogeneity, that is, different relaxation rates for solute molecules in different spatial regions. This hypothesis is tested with a new multidimensional spectroscopy, MUPPETS (multiple population-period transient spectroscopy). Rate heterogeneity is not found to be the primary cause of the dispersed kinetics. Rather, a homogeneous mechanism is responsible for this unusual phenomenon.
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Journal of Physical Chemistry Letters
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Physical Sciences not elsewhere classified
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