A study of the relation between translational and rotational diffusion through measurement of molecular recollision.

Translational and rotational diffusion rates of perdeuterated tempone (PDT) in ethanol are determined using electron paramagnetic resonance spectroscopy. The translational motion is measured on two scales: the macroscopic, as represented by the Heisenberg spin-exchange rate, and the microscopic, which entails recollisions between the same spin-exchange particle pair. The spin-exchange and recollision rates are used together to calculate the overall translational diffusion coefficient without recourse to assumptions concerning the value of the Stokes radius or collision distance. When observed as a function of solvent isothermal compressibility, the recollision time in ethanol is displaced from the common alkane curve at low temperatures but joins that curve at higher temperatures. Rotational correlation times in ethanol are obtained and show a decreasing rotation-translation coupling with increasing temperature, revealing a pattern that is qualitatively identical with respect to both collision and recollision. In comparison, an examination of PDT diffusion in toluene reveals an increasing rotation-translation coupling with increasing temperature. The contrasting behavior of the coupling in the two solvents is attributable to the degree of anisotropy in PDT rotation.