TY - JOUR
T1 - Electronic spectral shifts, reorganization energies, and local density augmentation of Coumarin 153 in supercritical solvents
AU - Biswas, R.
AU - Lewis, J. E.
AU - Maroncelli, M.
N1 - Funding Information:
The authors would like to thank Kenji Takahashi and Charles Jonah for sharing the results of their studies prior to publication, as well as helpful discussions on the analysis methods they employed, and also to Abby Robinson for her contributions to the initial stages of this work. Partial support of this research by the US Office of Naval Research is also gratefully acknowledged.
PY - 1999/9/10
Y1 - 1999/9/10
N2 - Solvent reorganization energies and local densities of Coumarin 153 (C153) in supercritical C2H6, CO2, and CHF3 (Tc=5 K) are measured using fluorescence spectroscopy. Reorganization energies are 320±70 and 770±70 cm-1 in CO2 and CHF3, respectively - nearly independent of density (0.3≤ρ/ρc≤2.1). The spectral shifts imply similar effective local densities in all three solvents. These effective densities can exceed 3-5 times the bulk density. In CO2 and CHF3, the maximum density augmentation calculated from emission shifts is ~20% greater than that calculated from excitation shifts. No such difference is found in C2H6.
AB - Solvent reorganization energies and local densities of Coumarin 153 (C153) in supercritical C2H6, CO2, and CHF3 (Tc=5 K) are measured using fluorescence spectroscopy. Reorganization energies are 320±70 and 770±70 cm-1 in CO2 and CHF3, respectively - nearly independent of density (0.3≤ρ/ρc≤2.1). The spectral shifts imply similar effective local densities in all three solvents. These effective densities can exceed 3-5 times the bulk density. In CO2 and CHF3, the maximum density augmentation calculated from emission shifts is ~20% greater than that calculated from excitation shifts. No such difference is found in C2H6.
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U2 - 10.1016/S0009-2614(99)00838-6
DO - 10.1016/S0009-2614(99)00838-6
M3 - Article
AN - SCOPUS:0000936535
SN - 0009-2614
VL - 310
SP - 485
EP - 494
JO - Chemical Physics Letters
JF - Chemical Physics Letters
IS - 5-6
ER -