Solvation dynamics of chromophores in polyethers

Steady-state and time-resolved optical techniques are employed to measure the solvation static and dynamics of large probe molecules in small polyethers. In ethylene glycol dimethyl ethers (n = 2, 3, and 4) we find that the solvation dynamics span from ∼50 fs to more than 100 ps. Three major time components can be resolved. The short time is bimodal with an ultrafast Gaussian component <70 fs followed by a ∼2 ps component. The second component of 10-20 ps depends on the polymer size and is attributed to segmental motion. The long component of > 100 ps is ascribed to cooperative motion of the polymer matrix.