When the Heterogeneous Appears Homogeneous: Discrepant Measures of Heterogeneity in Single Molecule Observables.

ABSTRACT

Supercooled liquids demonstrate stretched exponential relaxations consistent with the presence of spatially heterogeneous dynamics. Many experimental results are consistent with this picture, but differences in experimental approach may lead to different conclusions about the degree of heterogeneity in a given system. Here, we investigate whether observables accessible with single molecule (SM) approaches are consistent with each other and with ensemble measurements. In particular, the distribution of rotational relaxation times, τ(c), obtained from SM measurements is compared with the stretching exponent determined from a quasi-ensemble treatment of the same data. It is shown that the time-limited trajectories typical of SM experiments can lead to a stretching exponent that suggests homogeneous dynamics even in the presence of heterogeneous dynamics. After correction for the time-limited trajectories, additional discrepancy remains between stretching exponents measured via SM experiments and ensemble techniques. The remaining difference is attributed to the limited dynamic range of the SM experiments.