Spectroscopic Study and Simulation from Recent Structural Models for Eumelanin: I. Monomer, Dimers

Spectroscopic simulations of a leading structural model for melanin, the pigment responsible for coloration and photoprotection in humans and animals, were done. We performed density functional theory (DFT) calculations using both the local density approximation (LDA) and the generalized gradient approximation (GGA) on a recent structural model for eumelanin based on higher oligomers of the monomer of neutral 5,6-indolequinone and its reduced forms, semiquinone and hydroquinone. This paper reports on our semiempirical spectroscopic simulations for the monomer and dimer energy-minimized structures. Our second study (part II) extends this approach to higher oligomers (tetramers through hexamers) and points out that the known optical spectra of eumelanins can be adequately explained on this basis.