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Solvent Reorganizational Red-Edge Effect in Intramolecular Electron Transfer
Alexander P. Demchenko and Alexander I. Sytnik
Proceedings of the National Academy of Sciences of the United States of America
Vol. 88, No. 20 (Oct. 15, 1991), pp. 9311-9314
Published by: National Academy of Sciences
Stable URL: http://www.jstor.org/stable/2358137
Page Count: 4
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Polar solvents are characterized by statistical distributions of solute-solvent interaction energies that result in inhomogeneous broadening of the solute electronic spectra. This allows photoselection of the high interaction energy part of the distribution by excitation at the red (long-wavelength) edge of the absorption bands. We observe that intramolecular electron transfer in the bianthryl molecule from the locally excited (LE) to the charge-transfer (CT) state, which requires solvent relaxation and does not occur in vitrified polar solutions, is dramatically facilitated in low-temperature propylene glycol glass by the red-edge excitation. This allows one to obtain spectroscopically the pure CT form and observe its dependence upon the relaxational properties of the solvent. A qualitative potential model of this effect is presented.
Proceedings of the National Academy of Sciences of the United States of America © 1991 National Academy of Sciences