highlight 8 2019

Solvation dynamics control many ultrafast photochemical reactions, such as proton and electron transfer. Solvent mixtures that allow for the control of a single macroscopic solvent parameter (e.g. dielectric constant, viscosity or refractive index) are of key importance for detailed studies of solvent effects on such reactions. For this purpose, we are using a binary mixture of organic solvents. Such mixture allows for a selective control of polarity and relaxation times, while keeping viscosity and refractive index constant. Solvatochromism of standard push-pull dyes show a linear response with the orientational solvent polarity parameter,Δf, demonstrating the absence of any specific solvent interaction (Figures A and B). Furthermore, the rotational dynamics of coumarin 153, as measured from the fluorescence anisotropy decay, remain constant in the mixture (Figures B and C). This further supports the absence of any specific interactions and demonstrates the isoviscous nature of this mixture according to the Stokes-Einstein-Debye relation.

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Eric Vauthey

Physical Chemistry Department - Sciences II - University of Geneva
30, Quai Ernest Ansermet - CH-1211 Geneva 4 (Switzerland)

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