Solvent Effects upon Fluorescence Spectra and the Dipolemoments of Excited Molecules

A general formula for the difference of solvent shifts of fluorescence and absorption spectra in the approximation of long range dipolar interaction was derived using Ooshika’s theory of light absorption in solution. Measurements of fluorescence and absorption spectra of some naphthalene derivatives in various organic solvents were undertaken, and the data were analysed by the theoretical formula. The formula reproduces the experimental data satisfactorily, and from this fact it was concluded that the most predominant factor which determines the difference of solvent shifts of fluorescence and absorption spectra of these molecules is the interaction energy between solute and solvent molecules due to orientation polarization. The incremental values of dipolemoments in the excited state were estimated, and those for α-, β-naphthols and β-naphthyl methyl ether were interpreted as due to the increase of electron migration from the substituent in the excited state.