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J Chem Phys ; 140(24): 244904, 2014 Jun 28.
Article in English | MEDLINE | ID: mdl-24985675

ABSTRACT

We study the orientational properties of labeled segments in semiflexible dendrimers making use of the viscoelastic approach of Dolgushev and Blumen [J. Chem. Phys. 131, 044905 (2009)]. We focus on the segmental orientational autocorrelation functions (ACFs), which are fundamental for the frequency-dependent spin-lattice relaxation times T1(ω). We show that semiflexibility leads to an increase of the contribution of large-scale motions to the ACF. This fact influences the position of the maxima of the [1/T1]-functions. Thus, going from outer to inner segments, the maxima shift to lower frequencies. Remarkably, this feature is not obtained in the classical bead-spring model of flexible dendrimers, although many experiments on dendrimers manifest such a behavior.

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