Spectral diffusion in liquids with fluctuating solvent responses: Dynamical heterogeneity and rate exchange

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The effects of rate exchange mechanisms on time dependent inhomogeneous line widths associated with solvation dynamics were investigated. The heterogeneous character of the dynamics in supercooled liquids was modeled by associating a site specific solvent response function with each solute molecule. Time dependent moments obtained from simulations demonstrated that rate exchanged alters the time dependence of inhomogeneous optical linewidths. For both distributed and single valued exchange rates with average exhange times near the average relaxation time, the calculated spectral diffusion remained incompatible with the data.

Original languageEnglish (US)
Pages (from-to)1429-1434
Number of pages6
JournalJournal of Chemical Physics
Issue number3
StatePublished - Jul 15 2001


ASJC Scopus subject areas

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

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