Characterization of Internal Reorientation of Methyl Group in 2,6-Dichlorotoluene

Abstract

The two correlation times previously obtained in our coupled relaxation measurement for the methyl group in 2,6-dichlorotoluene may be used as a criterion for evaluating the reorientation dynamics of an internal rotor. We numerically tested an extended diffusion model and the Smoluchowski diffusion equation to see how the rotational inertial effect and jump character contribute to the internal correlation time ratio of the internal rotor. We also analytically solved the general jump model with three different rate constants in a sixfold symmetric potential barrier. By assuming that the internal rotation of the methyl group in 2,6-dichlorotoluene can be described in terms of jumps among sixfold harmonic potential wells, we can conclude that the jump model satisfactorily reproduce the experimental data and the rate for sixfold jump is at least 1.53 times as great as that of a threefold jump.