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J Phys Chem B. 2008 Mar 20;112(11):3390-6. doi: 10.1021/jp7107126. Epub 2008 Feb 26.

Dynamic solvation in phosphonium ionic liquids: comparison of bulk and micellar systems and considerations for the construction of the solvation correlation function, C(t).

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  • 1Department of Chemistry, Iowa State University, Ames, Iowa 50011, USA.


Dynamic solvation of the dye coumarin 153 is studied in a phosphonium ionic liquid: hexadecyltributylphosphonium bromide, [(C4)3C16P+][Br-]. It forms micelles in water, and the bulk also exists as a liquid under our experimental conditions. This system permits a comparison with an imidazolium ionic liquid studied earlier, which also formed micelles in water (J. Phys. Chem. A 2006, 110, 10725-10730). We conclude that our analysis of the comparable situation in a phosphonium liquid is not as definitive as we had proposed earlier, i.e., that the majority of the early-time solvation arises from the organic cation. Part of the difficulty in performing this analysis is most likely due to the amount of water that is associated with the micelle. In the course of this work, we have focused on the calculation of the solvation correlation function, C(t), and investigated how it depends upon the methods with which the "zero-time" spectrum is constructed.

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