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David von Seggern, Christian Spitz, Ralf Menzel

Free Volume Nanocavities in PMMA Revealed by Rotational Dephasing of Paraterphenyl in a Transient Grating Experiment

Keywords: transient grating spectroscopy, PMMA, free volume, nonpolar dopant

The excited state decay behaviour of p-terphenyl in cyclohexane solution and in a rigid poly(methyl methacrylate) (PMMA) film is reported as measured in a ps polarization dependent transient grating experiment. In both cases, the diffracted intensity shows a biexponential decay. The slower component is attributed to excited state lifetime. In the liquid solution, the faster decay component is described by the hydrodynamical Stokes–Einstein–Debye theory for rotational reorientation under slip boundary conditions. In the rigid matrix it is interpreted in terms of a free volume effect.

Zeitschrift für Physikalische Chemie, Oldenbourg Wissenschaftsverlag

Print ISSN: 0942-9352
Volume: 221, 04/2007
Pages: 527 - 536

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