Carotenoids are conjugated linear molecules built from the repetition of terpene units, which display a large structural diversity in nature. They may, in particular, contain several types of side or end groups, which tune their functional properties, such as absorption position and photochemistry. We report here a detailed experimental study of the absorption and vibrational properties of allene-containing carotenoids, together with an extensive modeling of these experimental data. Our calculations can satisfactorily explain the electronic properties of vaucheriaxanthin, where the allene group introduces the equivalent of one C═C double bond into the conjugated C═C chain. The position of the electronic absorption of fucoxanthin and butanoyloxyfucoxanthin requires long-range corrections to be found correctly on the red side of that of vaucheriaxanthin; however, these corrections tend to overestimate the effect of the conjugated and nonconjugated C═O groups in these molecules. We show that the resonance Raman spectra of these carotenoids are largely perturbed by the presence of the allene group, with the two major Raman contributions split into two components. These perturbations are satisfactorily explained by modeling, through a gain in the Raman intensity of the C═C antisymmetric stretching mode, induced by the presence of the allene group in the carotenoid C═C chain.

Biology Centre Czech Academy of Sciences Branisovska 31 370 05 Ceske Budejovice Czech Republic

Faculty of Science University of South Bohemia Branisovska 1760 370 05 Ceske Budejovice Czech Republic

Institute for Integrative Biology of the Cell CEA CNRS Université Paris Saclay 91198 Gif sur Yvette France

Institute of Chemical Physics Faculty of Physics Vilnius University Saulėtekio Avenue 3 LT 10222 Vilnius Lithuania

Molecular Compounds Physics Department Center for Physical Sciences and Technology Sauletekio Avenue 3 LT 10257 Vilnius Lithuania

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