화학공학소재연구정보센터
Journal of Physical Chemistry A, Vol.112, No.18, 4186-4193, 2008
Experimental and theoretical analysis of the reorientational dynamics of fullerene C-70 in various aromatic solvents
A previous study Of C-70 in deuterated chlorobenzene generated evidence suggesting C-70 was experiencing unique reorientational behavior at given temperatures. The present study explores the possibility that this behavior is present across other solvents. The C-13 spin-lattice relaxation rates for four carbon resonances in C-70 were analyzed in benzene-d(6), chlorobenzene-d(5), and o-dichlorobenzene-d(4), and as a function of temperature, to probe the reorientational dynamics of this fullerene. Anisotropic behavior was observed at the lowest (283 K) and highest temperatures (323 K), isotropic diffusion was seen between 293 and 303 K, and quasi-isotropic at 313 K. When anisotropic motion was present, diffusion about the figure axis was seen to be higher than diffusion of the figure axis. Experimentally obtained diffusion coefficients generated reorientational correlation times that were in excellent agreement with experimental values. Theoretical predictions generated by a modified Gierer-Wirtz model provided acceptable predictions of the diffusion constants; with D-X usually being more closely reproduced and D-Z values generally being underestimated. Overall, the results indicate that the factors affecting rotational behavior are complex and that multiple solvent factors are necessary to characterize the overall motion Of C-70 in these solvents. Although a solvent's viscosity is normally sufficient to characterize the tumbling motion, the spinning motion is less sensitive to solvent viscosity but more responsive to solvent structure. The balance and collective influence of these factors ultimately determines the overall rotational behavior.