Enhanced translation of probe molecules in supercooled o-terphenyl: Signature of spatially heterogeneous dynamics?

Abstract

A holographic fluorescence recovery after photobleaching technique has been used to measure translational diffusion coefficients DT for four probes in supercooled o-terphenyl (OTP). DT values from 10−6 to 10−14 cm2/s were observed in the temperature range from Tg+8 K to Tg+90 K (Tg=243 K). In agreement with previous reports, the translational diffusion of probe molecules which are the same size as OTP molecules has a significantly weaker temperature dependence than T/η. However, as the size of the probe molecule is increased the temperature dependence of DT tracks T/η increasingly well. The transition between a weak temperature dependence to that of T/η occurs over only a factor of 3 in probe size. Previous work established that the rotational correlation times τc of these four probes in OTP tracks η/T. The product DTτc is independent of temperature for the largest probe but increases almost 2 orders of magnitude for the smaller probes as Tg is approached. A strong correlation is observed between this enhancement of translational diffusion and the KWW β values obtained from rotation measurements; probes with small β values show enhanced translation. These observations are qualitatively explained by spatially heterogeneous dynamics. The probes studied are rubrene, 9,10-bis(phenylethynyl)anthracene, tetracene, and anthracene.