Relations between the Raman spectra and molecular structure of selected carotenoids: DFT study of α-carotene, β-carotene, γ-carotene and lycopene.

Using the density functional theory (DFT), we calculated the structures and Raman spectra of trans-isomers of α-carotene, β-carotene, γ-carotene and lycopene as well as trans-isomers of modified β-carotene and lycopene molecules with substituted end or/and side groups. The DFT calculations showed that the position of the CC stretching band depends mainly on the number of conjugated CC bonds and decreases with an increase in the conjugation length. The weak dependence of the position of the CC stretching band on the structure of the carotenoid side and end groups suggests that this band can be used to evaluate the conjugation length for trans-isomers of various molecules containing polyene chains. The CC stretching band shifts towards lower wavenumbers with growth of the conjugation length or masses of the end groups and to higher wavenumbers in the presence of the side CH groups. The intensities of the CC and CC stretching bands are enhanced with growth of the conjugation length or masses of the end groups. The presence of the side CH groups results in bending of the carotenoid backbone, splitting and dumping of intensities of the CC and CC stretching bands.