Biphasic rate exchange in supercooled o -terphenyl from an ensemble analysis of single-molecule data

Abstract

Heterogeneity in relaxation rates is a key feature of supercooled liquids. It implies the existence of a rate-exchange process to restore ergodicity, but the experimental characterization of that exchange has been incomplete and controversial. Here, a recently proposed, ensemble-based analysis is applied to single-molecule dichroism data to extract a detailed correlation function for rotational-rate exchange. A large, late phase is $8.7\ifmmode\pm\else\textpm\fi{}0.3$ times slower than the probe rotation and 22 times the alpha-relaxation time, and it has its own exchange-rate dispersion. A small, early phase tracks the initial rotational decay. We propose that the late phase is due to molecules in the core of spatial regions of correlated rates and that the early phase is due to molecules on the boundaries. The results imply that multiple processes and spatial fields are involved in the primary relaxation in supercooled liquids.