Temperature-dependent rotational relaxation in a viscous alkane: Interplay of shape factor and boundary condition on molecular rotation

Rotational relaxation of three organic solutes, coumarin 6 (C6), 2,5-dimethyl-1, 4-dioxo3,6-diphenylpyrrolo[3,4-c]pyrrole (DMDPP), and nile red (NR), that are similar in size but distinct in shape has been studied in a nonpolar solvent, squalane as a function of temperature to find out how the mechanical friction experienced by the solute molecule is influenced by its shape. It has been observed that C6 rotates slowest followed by NR and DMDPP. The results are analyzed using Stokes–Einstein–Debye (SED) hydrodynamic theory and also quasihydrodynamic theories of Gierer and Wirtz, and Dote, Kivelson, and Schwartz. Analysis of the data using the SED theory reveals that the measured reorientation times of C6 and DMDPP follow subslip behavior whereas those of NR are found to match slip predictions. While no single model could mimic the observed trend even in a qualitative manner, the reorientation times of C6 and DMDPP when normalized by their respective shape factors and boundary-condition parameters can be scaled on a common curve over the entire range of temperature studied. The probable reasons for the distinctive rotational behavior of NR as compared to C6 and DMDPP are explained in terms of its molecular shape and how this in turn influences the boundary-condition parameter are discussed.