Spectral broadening and its effect in Stark spectra of carotenoids

Electrooptical parameters of eight carotenoids with different molecular structures were determined from the absorption and electroabsorption (Stark) spectra in glassy solvents and in poly(methyl methacrylate) films at temperatures 108-115 K. The results point to a limited significance of solvent-induced dipole moments in carotenoids resulting from local electric fields generated by solvent molecules, and indicate that the features in Stark spectra related to apparent dipole moments display a correlation with the bandwidth of individual vibronic transitions in absorption spectra. Model calculations show that it is possible to describe the Stark spectra by assuming a close link between the molecular polarizability and the inhomogeneous spectral shift. It is postulated that the dipole-related features in Stark spectra and the inhomogeneous broadening have a common origin in the distortions of molecular geometry in the form of torsional deformations about the single C-C bonds. (C) 2001 Published by Elsevier Science B.V.