TY - JOUR
T1 - Analysis of the decay of the fluorescence anisotropy of 2,4,6,8-decatetraene in a viscous hydrocarbon solution
T2 - the off-axis orientation of the transition dipole moment
AU - Dou, Xiumei
AU - Shang, Quan yuan
AU - Hudson, Bruce S.
PY - 1992/1/24
Y1 - 1992/1/24
N2 - The time dependence of the anisotropy of all-trans-decatetraene in paraffin oil solution is analyzed in terms of a prolate ellipsoid of revolution with the electronic transition dipole oriented at an angle with respect to the ellipsoidal long axis. Data obtained at five temperatures from 10 to -5°C are all well fit by this model and in each case an angle of 22±2° is obtained. This value is in good agreement with other recent results using a single crystal containing a tetraene chromophore. The values of the parallel and perpendicular rotational diffusion coefficients vary smoothly with temperature. These are discussed in terms of the molecular dimensions and hydrodynamic slip versus stick boundary conditions. The end-over-end motion is found to be described by diffusion with slip boundary conditions; the axial motion is much faster than expected on the basis of stick boundary conditions but much slower than for slip conditions.
AB - The time dependence of the anisotropy of all-trans-decatetraene in paraffin oil solution is analyzed in terms of a prolate ellipsoid of revolution with the electronic transition dipole oriented at an angle with respect to the ellipsoidal long axis. Data obtained at five temperatures from 10 to -5°C are all well fit by this model and in each case an angle of 22±2° is obtained. This value is in good agreement with other recent results using a single crystal containing a tetraene chromophore. The values of the parallel and perpendicular rotational diffusion coefficients vary smoothly with temperature. These are discussed in terms of the molecular dimensions and hydrodynamic slip versus stick boundary conditions. The end-over-end motion is found to be described by diffusion with slip boundary conditions; the axial motion is much faster than expected on the basis of stick boundary conditions but much slower than for slip conditions.
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U2 - 10.1016/0009-2614(92)85151-Y
DO - 10.1016/0009-2614(92)85151-Y
M3 - Article
AN - SCOPUS:0039265642
VL - 189
SP - 48
EP - 53
JO - Chemical Physics Letters
JF - Chemical Physics Letters
SN - 0009-2614
IS - 1
ER -