Molecular motions in liquid. I. Rotation of water and small alcohols studied by deuteron relaxation

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Abstract
The deuteron spin lattice relaxation time T1 of CH3OD, C2H5OD, (CH3)2CHOD, and (CH3)3CHOD is reported as a function of temperature and frequency. The deuteron T1 of the alcohols in dilute benzene solutions was also measured at 25°C. A detailed analysis of the experimental results and other magnetic and dielectric relaxation data from the literature was made. Based upon the analysis, it is suggested that the success of the Debye model in explaining the dielectric and magnetic relation behavior of water and small alcohols may be purely coincidental. It seems that the error in applying Stokes law for the rotation of a macroscopic sphere to small molecules in liquid and the error in assuming that water and alcohols rotate as monomers largely cancel each other, yielding much better apparent agreement between calculated and experimental data than those for nonassociating liquids. The deuteron T1’s for the alcohols are further analyzed in terms of anisotropic rotation.