1. Experimental and Theoretical Analysis of the Reorientational Dynamics of Fullerene C70 in Various Aromatic Solvents
- Author
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Robert M. Hughes, Bartolotti L, Mutzenhardt P, Rodriguez Aa, Departement of Biochemistry, Duke University [Durham], Structure et Réactivité des Systèmes Moléculaires Complexes (SRSMC), Institut de Chimie du CNRS (INC)-Université de Lorraine (UL)-Centre National de la Recherche Scientifique (CNRS), Departement of Chemistry, East Carolina University [Greenville] (ECU), and University of North Carolina System (UNC)-University of North Carolina System (UNC)
- Subjects
Models, Molecular ,Fullerene ,Time Factors ,Rotation ,Thermodynamics ,010402 general chemistry ,01 natural sciences ,Diffusion ,chemistry.chemical_compound ,Viscosity ,0103 physical sciences ,Organic chemistry ,Physical and Theoretical Chemistry ,Diffusion (business) ,010306 general physics ,Anisotropy ,Relaxation (NMR) ,Isotropy ,Temperature ,Benzene ,3. Good health ,0104 chemical sciences ,Solvent ,[CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry ,Kinetics ,chemistry ,Chlorobenzene ,Solvents ,Fullerenes - Abstract
International audience; A previous study of C70 in deuterated chlorobenzene generated evidence suggesting C70 was experiencing unique reorientational behavior at given temperatures. The present study explores the possibility that this behavior is present across other solvents. The 13C spin-lattice relaxation rates for four carbon resonances in C70 were analyzed in benzene-d6, chlorobenzene-d5, and o-dichlorobenzene-d4, 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 DX usually being more closely reproduced and DZ 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 C70 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.
- Published
- 2008
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