Excited state dipole moments of N,N-dimethylaniline from thermochromic effect on electronic absorption and fluorescence spectra

The effect of temperature on absorption and fluorescence spectra of N,N-dimethylaniline (DMA) in ethyl acetate has been studied for temperature ranging from 293 to 388 K. The permittivity ε and refractive index n of the solvent decrease with temperature increase and the absorption and fluorescence bands are blue shifted (so-called “thermochromic shift”). Based on this phenomenon, the dipole moment μ_e in the excited singlet state and the Onsager interaction radius a for DMA were determined using the Bilot and Kawski theory [L. Bilot, A. Kawski, Z. Naturforsch. 17a (1962) 621; 18a (1963) 10, 256].

For the known dipole moment in the ground state μ_g = 1.61 D and for /a³ = 0.54 ( is the polarizability of the solute) the average value of μ_e = 3.55 D and a = 3.1 Å were determined. The obtained values for DMA are compared with the experimental values determined by other authors.