ABSORPTION SPECTRAL SHIFTS OF CAROTENOIDS RELATED TO MEDIUM POLARIZABILITY

Abstract

Abstract–Solvent induced absorption spectral shifts of the electronic transition from ground 1 Ag state to the excited 1Bu state in carotenoids have been studied. It is shown that the shift depends only on dispersion interactions in non‐polar solvents. In polar media there is just a small extra contribution to the red‐shift, due to other forms of interactions. The spectral shifts are well described by the theory, which expresses the shift relative to the gas phase value, as a function of solvent polarizability. The main conclusion is that the dominating mechanism behind the large red‐shifted absorbance of carotenoids in the proteinacous environment, in vivo, is the mutual polarizability interactions between the carotenoids and the surrounding medium. The solution‐phase values of the dipole moments of the lAg to 1Bu transitions and the differences of isotropic polarizability between 1Bu and lAg states of carotenoids in non‐polar solvents are calculated and found to be around 13 D and 360 Å3 respectively. From the great overlap of absorption spectra between carotenoids in quinoline and carotenoids in vivo in purple bacterial antenna complexes, it can be expected that the carotenoids are surrounded by several aromatic amino acids in vivo. Comparisons have been done between the exicted states in carotenoids and in linear conjugated polyenes.