Rotational diffusion of a nonpolar and a dipolar solute in 1-butyl-3-methylimidazolium hexafluorophosphate and glycerol: interplay of size effects and specific interactions.

Temperature dependent rotational diffusion of a nonpolar solute, 9-phenylanthracene (9-PA), and a dipolar solute, rhodamine 110 (R110), has been examined in an ionic liquid, 1-butyl-3-methylimidazolium hexafluorophosphate ([bmim(+)][PF(6) (-)]) and in a conventional solvent, glycerol. This study has been undertaken to explore how parameters such as solvent size and free volume influence solute rotation in the case of a nonpolar solute, 9-PA. To understand the role of specific solute-solvent interactions, similar measurements have been performed with a dipolar analogue, R110. It has been observed that the viscosity normalized reorientation times of 9-PA are longer by a factor of 1.4-1.6 in glycerol compared to those in [bmim(+)][PF(6) (-)]. While the most commonly used Stokes-Einstein-Debye hydrodynamic theory is not successful in explaining this experimental observation, Gierer-Wirtz and Dote-Kivelson-Schwartz quasihydrodynamic theories could rationalize this trend, albeit in a qualitative manner. Rotational diffusion of R110, on the other hand, follows an exactly opposite trend compared to 9-PA. The normalized reorientation times of R110 are longer by a factor of 1.3-1.4 in [bmim(+)][PF(6) (-)] compared to glycerol, which is due to the formation of stronger solute-solvent hydrogen bonds between the positively charged R110 and the ionic liquid.