1. Rotational Dynamics of Coumarin 153 in Supercritical Fluoroform
- Author
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Kimihiko Hara, Yoshiro Yonezawa, Yuji Hoshihara, Okitsugu Kajimoto, Naoki Ito, and Noritsugu Kometani
- Subjects
Solvent ,chemistry.chemical_compound ,Fluoroform ,Chemistry ,Computational chemistry ,Analytical chemistry ,Extrapolation ,Polar ,Physical and Theoretical Chemistry ,Rotation ,Fluorescence ,Fluorescence anisotropy ,Supercritical fluid - Abstract
Subpicosecond fluorescence anisotropy decay curves have been measured using the fluorescence up-conversion technique to examine the rotational dynamics of coumarin 153 (C 153) in supercritical fluoroform (T = 302 and 310 K). For reduced densities (p, = ρ/ρ c ) above 0.9, the rotation times of C153 increase with density. For reduced densities lower than 0.9, the rotation times increase with decreasing density and has a maximum at a density near p, = 0.5. The comparison with the extrapolation of the data in polar aprotic solvents indicates that the local solvent density around the solute exceeds about 4 times the bulk density at a density near ρ r = 0.5, which is consistent with those obtained from the steady-state electronic spectral shifts.
- Published
- 2004