Nuclear Spin Relaxation in Liquids. Spheroidal Molecules

Abstract

Nuclear spin—lattice relaxation times have been measured as a function of temperature for a number of liquid hydrocarbons. These data, together with other available measurements on rigid, spheroidal molecules, are compared with the Bloembergen, Purcell, and Pound (B.P.P.) theory of spin—lattice relaxation in liquids, and it is shown that the B.P.P. calculation of the rotational contribution to the relaxation time gives a value which are much shorter than the total experimental relaxation times. It is then assumed that the time dependence of the rotational angular autocorrelation functions of these molecules is dominated by dynamical coherence, rather than by frictional forces as assumed in the B.P.P. theory. If one calculates the net spin—lattice relaxation time T₁ by summing the translational contribution calculated from the B.P.P. theory and the rotational contribution calculated from an approximate autocorrelation function valid for small but nonzero friction constants, one obtains values for T₁ which are in quantitative agreement with the data for nonpolar, spheroidal molecules. Furthermore, when the two calculations are compared with the data for polar spheroidal molecules, it is seen that frictional forces are the predominant factor in the rotational motion of these systems, but the values obtained for the rotational friction constant from the Stokes—Einstein equation are in error by a considerable amount.