Effect of the solvent density and species on the back-electron transfer rate in the hexamethylbenzene/tetracyanoethylene charge-transfer complex

The back-electron transfer (b-ET) process in the hexamethylbenzene/tetracyanoethylene charge-transfer complex was studied by the transient absorption spectroscopy in several fluids (ethane, nitrous oxide, carbon dioxide, and trifluoromethane) from the critical density to twice that of it at 323.2 K. The b-ET rate was determined by the decay rate of the excited state absorption. The b-ET rate increased with the increase of solvent density in carbon dioxide and nitrous oxide. The b-ET rate also increased in the order of ethane, nitrous oxide, carbon dioxide, and trifluoromethane, compared at the similar reduced density divided by the solvent critical density. Based on the formulation by Marcus and Jortner, the reaction free energy and the solvent reorganization energy were estimated from the change of the absorption spectrum relative to the gaseous phase spectrum, simply by assuming that the intramolecular reorganization energy does not depend on the solvent density and the species. The reaction free energy and the solvent reorganization energy in fluids obtained in this way were almost linearly correlated, and the density dependence was larger in the lower density region. The b-ET rates in various conditions showed a good correlation with the reaction free energy estimated from the spectral simulation. The b-ET rate showed a significant isotope effect by perdeuteriation of hexamethylbenzene as is predicted by the fluorescence quantum yield [K. Kulinowski et al., J. Phys. Chem. 99, 17715 (1995)], which could not be reproduced by this model. (C) 1998 American Institute of Physics. [S0021-9606(98)52604-9].