Excited state properties of the astaxanthin radical cation: A quantum chemical study

Using time-dependent density functional theory, the excited electronic states of the astaxanthin radical cation (AXT+) are investigated. While the optically allowed excited D1 and D3 states are typical ππ∗ excited states, the D2 and D4 states are nπ∗ states. Special emphasis is put onto the influence of the carbonyl groups onto the excited states. For this objective, the excited states of four hypothetical carotenoids and zeaxanthin have been computed. Addition of a carbonyl group to a conjugated carbon double bond system does essentially not change the vertical excitation energies of the optically allowed ππ∗ states due to two counter-acting effects: the excitation energy should increase due to the -M-effect of the carbonyl group and at the same time decrease owing to the elongation of the conjugated double bond system by the carbonyl group itself.