Solvent response and dielectric relaxation in supercooled butyronitrile

Naoki Ito, Kalyan Duvvuri, Dmitry Matyushov, Ranko Richert

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Abstract

We have measured the dynamics of solvation of a triplet state probe, quinoxaline, in the glass-forming dipolar liquid butyronitrile near its glass transition temperature T 8=95 K. The Stokes shift correlation function displays a relaxation time dispersion of considerable magnitude and the optical linewidth changes along the solvation coordinate in a nonmonotonic fashion. These features are characteristic of solvation in viscous solvents and clearly indicate heterogeneous dynamics, i.e., spatially distinct solvent response times. Using the dielectric relaxation data of viscous butyronitrile as input, a microscopic model of dipolar solvation captures the relaxation time, the relaxation dispersion, and the amplitude of the dynamical Stokes shift remarkably well.

Original languageEnglish (US)
Article number024504
JournalJournal of Chemical Physics
Volume125
Issue number2
DOIs
StatePublished - Jul 26 2006

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ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

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