Understanding/unravelling carotenoid excited singlet states

Carotenoids are essential light-harvesting pigments in natural photosynthesis. They absorb in the blue-green region of the solar spectrum and transfer the absorbed energy to (bacterio-)chlorophylls, and thus expand the wavelength range of light that is able to drive photosynthesis. This process is an example of singlet-singlet excitation energy transfer, and carotenoids serve to enhance the overall efficiency of photosynthetic light reactions. The photochemistry and photophysics of carotenoids have often been interpreted by referring to those of simple polyene molecules that do not possess any functional groups. However, this may not always be wise because carotenoids usually have a number of functional groups that induce the variety of photochemical behaviours in them. These differences can also make the interpretation of the singlet excited states of carotenoids very complicated. In this article, we review the properties of the singlet excited states of carotenoids with the aim of producing as coherent a picture as possible of what is currently known and what needs to be learned.