The dynamics of heterogeneities in glasses probed with single molecule spectroscopy

PHYS 326

Rachel Allen, Rachel.M.Allen@williams.edu1, Aashish Adhikari, aashish@uchicago.edu2, and Dieter Bingemann, Dieter.Bingemann@williams.edu1. (1) Department of Chemistry, Williams College, 47 Lab Campus Drive, Williamstown, MA 01267, (2) present address, Department of Chemistry, The University of Chicago
With single molecule spectroscopy we probe the dynamics of local environments in glasses, which is characterized by a spatially heterogeneous rate of rearrangement within a local environment, the relaxation rate, and the rate of exchange between environments, the lifetimes of these heterogeneities. With different probe molecules in polyvinyl acetate, we determine both rates close to the glass transition temperature using correlation analysis. The temperature dependence of the relaxation times agrees well with dielectric experiments from the literature, the absolute time scales from our single molecule experiments are slower by a constant factor that depends on the size of the probe molecule: from 80-fold for Rhodamine B to about 5-fold for the smaller iodine. The ratio of observed single molecule reorientation times to heterogeneity lifetimes is close to one for both probe molecules at all investigated temperatures.