NMR relaxation of the orientation of single segments in semiflexible dendrimers.

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. [ABSTRACT FROM AUTHOR]