Vibrational Relaxation in Carotenoids as an Explanation for Their Rapid Optical Properties

We propose the ultrafast S2 (1Bu) to S1 (2Ag) “electronic internal conversion” observed in carotenoids to be a vibrational relaxation of the 1Bu state. This suggestion arises from comparing excited-state geometries computed with the CAM-B3LYP density functional to the ground states; it is found that each conjugated atom moves less than 5 pm in, for example, violaxanthin. However, the changes of excitation energies are large, ranging from 0.4 to 1.2 eV. This is connected to the size of the conjugated system: while each atom contributes only 0.02–0.06 eV, the sum amounts to the observed shift. Additional analysis of computational data is provided from new or already published calculations. As the mechanism may be valid for all linear polyenes, the model has implications that go beyond the presented case of carotenoids. Finally, four sets of experimental data on carotenoids published elsewhere are reinterpreted. The model predicts near-infrared (IR) absorptions and transient femtosecond IR spectra within 0.1 eV accuracy