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Slow dynamics in an azopolymer molecular layer studied by x-ray photon correlation spectroscopy

We report the results of X-ray photon correlation spectroscopy (XPCS) experiments on Langmuir Blodgett multilayers of a photosensitive azo-polymer. Time correlation functions have been measured at different temperatures and momentum transfers (q) and under different illumination conditions (darkness, UV or visible). The correlation functions are well described by the Kohlrausch-Williams-Watts (KWW) form with relaxation times that are proportional to q^-1, which in other systems have been explained in terms of intermittent rearrangements [L. Cipelletti et al., Phys. Rev. Lett. 84, 2275-2278 (2000)] or random dipolar interactions within an elastic medium [J.- P. Bouchaud and E. Pitard, Eur. Phys. J. E 6, 231-236 (2001)]. The characteristic relaxation times follow the well known Vogel-Fulcher-Tammann law describing the temperature dependence of the bulk viscosity of this polymer. UV photoperturbation accelerates the relaxation dynamics, in qualitative agreement with the fluidification effect of UV photo-perturbation previously observed by surface rheometry, and is used to drive the system out of equilibrium. Transient dynamics is characterized, by the variance chi of the two-times correlation functions. A clear peak in chi appears at a well defined time tau_C which scales with q^-1 and with the ageing time, in a similar fashion as previously reported in colloidal suspensions [O. Dauchot et al., Phys. Rev. Lett. 95, 265701 (2005)]. From an accurate analysis of the correlation functions we could demonstrate a temperature dependent cross-over from KWW compressed to simple exponential behaviour, which is modified by the fluidification due to the optical pumping of the cis-trans isomerisation of the side-chain azobenzene group.