The solute size effect in rotational diffusion experiments: A test of microscopic friction theories

The experimentally measured rotational diffusion times of various neutral solute molecules are compared with hydrodynamic and molecular models for microscopic friction. New viscosity and temperature dependent results for the rotational time of a large neutral solute (26 Å long) indicate nearly perfect agreement with stick hydrodynamic predictions in both alkane and alcohol solvents. For smaller solute molecules, the results of previous studies show an increasingly large deviation from hydrodynamic predictions as the solute size decreases. This solute size dependent effect is compared with the theoretical predictions of Zwanzig’s hydrodynamic ‘‘bumpy cylinder’’ model, Dote–Kivelson-Schwartz’s molecular free volume model, and a new generalized hydrodynamic model for the effects of frequency dependent viscosity on molecular rotational diffusion. Although hydrodynamic predictions agree with experiment in some respects, it is found that molecular aspects of the solvation process must be introduced in order to get quantitative agreement with the observed solute size dependence.