Local viscosity of supercooled glycerol near Tg probed by rotational diffusion of ensembles and single dye molecules.
We probe the rotational diffusion of a perylene dye in supercooled glycerol, 5-25 K above the glass-transition temperature (T(g) = 190 K) at the ensemble and the single-molecule level. The single-molecule results point to a broad distribution of local viscosities that vary by a factor of five or more for different individual fluorophores at a given temperature. By following the same single molecules at various temperatures, we find that the distribution of local viscosities itself broadens upon approaching T(g). This spatial heterogeneity is found to relax extremely slowly, persisting over hours or even days. These results convey a picture of heterogeneous liquid pockets separated by solid-like walls, which exist already well above the viscosimetric glass transition.
Zondervan
Rob
R
Molecular Nano-Optics and Spins, Huygens Laboratory, Leiden University, Niels Bohrweg 2, 2333 CA Leiden, The Netherlands.
Kulzer
Florian
F
Berkhout
Gregorius C G
GC
Orrit
Michel
M
D004058:Diffusion; D005456:Fluorescent Dyes / Q000737:chemistry*; D005898:Glass / Q000737:chemistry*; D005990:Glycerol / Q000737:chemistry*; D015394:Molecular Structure; D044367:Phase Transition; D012399:Rotation; D013696:Temperature; D013816:Thermodynamics; D014783:Viscosity
D005456:Fluorescent Dyes; D005990:Glycerol