Complete breakdown of the Debye model of rotational relaxation near the   isotropic-nematic phase boundary: Effects of intermolecular correlations in   orientational dynamics
  The Debye-Stokes-Einstein (DSE) model of rotational diffusion predicts that the rotational correlation times $\tau_{l}$ vary as $[l(l+1)]^{-1}$, where $l$ is the rank of the orientational correlation function (given in terms of the Legendre polynomial of rank $l$). One often finds significant deviation from this prediction, in either direction. In supercooled molecular liquids where the ratio $\tau_{1}/\tau_{2}$ falls considerably below three (the Debye limit), one usually invokes a jump diffusion model to explain the approach of the ratio $\tau_{1}/\tau_{2}$ to unity. Here we show in a computer simulation study of a standard model system for thermotropic liquid crystals that this ratio becomes much less than unity as the isotropic-nematic phase boundary is approached from the isotropic side. Simultaneously, the ratio $\tau_2/\eta$ (where $\eta$ is the shear viscosity of the liquid) becomes {\it much larger} than hydrodynamic value near the I-N transition. We have also analyzed the break down of the Debye model of rotational diffusion in ratios of higher order rotational correlation times. We show that the break down of the DSE model is due to the growth of orientational pair correlation and provide a mode coupling theory analysis to explain the results. 
Prasanth P. Jose, Dwaipayan Chakrabarti and Biman Bagchi