Experimental correlation of nitroxide recollision spin exchange with free volume and compressibility in alkane and...

Diffusion of perdeuterated tempone (PDT) in various nonpolar hydrocarbon solvents on both the large and microscopic scales is examined through electron paramagnetic resonance spectroscopy. Spectral line broadening and hyperfine spacing are measured in order to extract both the Heisenberg spin-exchange rate as well as the average recollision times between spin-probe pairs. Probe recollision is responsible for a linear component to the dependence of the line shift on spectral broadening which has been identified in recent years. The present study extends the work of a previous paper by Kurban et al. [J. Chem. Phys. 129, 064501 (2008)], in which it was reported that recollision rates for PDT formed a common curve across n-alkanes when plotted with respect to free volume and to isothermal compressibility. It is now found that such common curves occur within distinct chemical families, in particular, the alkane and aromatic groups. Within each chemical family, the spin probe recollision rate correlates with free volume and compressibility independently of the geometry of the particular solvent. All solvents show significantly enhanced recollisional diffusion over the Stokes-Einstein (SE) prediction at high temperatures. The spin-exchange rate forms a common curve with respect to T/eta for all alkanes except cyclohexane and another common curve in all three aromatic compounds. It is reasoned that although all spin-exchange rates are near to the SE prediction, the semblance of hydrodynamic behavior is superficial and arises incidentally from mathematical cancellation of terms in a generalized diffusion coefficient. As a collision pair coexists for a time within a solvation shell, the recollision time places a lower limit on the lifetime of the solvent cage. Although molecular dynamics simulations conducted thus far have yielded cage lifetimes lower than the measured recollision times, this is attributable to the fact that such simulations have mostly examined cage configurations too small to harbor a spin-exchange encounter, and is also likely due to restrictive mathematical definitions of cage lifetimes that are employed in such simulations.