Nonresonant dielectric hole burning in neat and binary organic glass formers -: art. no. 224511

Binary mixtures of the molecular glass former 2-picoline in oligostyrene, in which the dielectric response of 2-picoline exhibits a particularly broad distribution of correlation times, are investigated by nonresonant dielectric hole-burning (NDHB) spectroscopy and the results are compared with NDHB in neat systems, in particular, glycerol. It turns out that in both substance classes spectral selectivity is achieved, which indicates that dynamics is heterogeneous, i.e., slow and fast responses coexist in the material. However, in binary systems the position of the spectral modifications is completely determined by the spectral density of the pump field, and thus shifts linearly with burn frequency as expected, also at pump frequencies around the alpha-relaxation maximum. It is shown that in binary systems the lifetime tau(rec) of the spectral modifications is determined by the burn frequency omega(p) and exceeds its inverse by about one order of magnitude, indicating long-lived dynamic heterogeneity. The data are described in terms of a previously suggested model of dynamically selective heating, which was extended to include intrinsic nonexponential relaxation. It turns out that the spectral broadening in binary mixtures is not only due to pronounced dynamic heterogeneity, but partially also due to intrinsic broadening of the relaxation function.