Ultrafast time-resolved absorption spectroscopy of geometric isomers of xanthophylls

This paper presents an ultrafast optical spectroscopic investigation of the excited state energies, lifetimes and spectra of specific geometric isomers of neoxanthin, violaxanthin, lutein, and zeaxanthin. All-trans- and 15,15′-cis-β-carotene were also examined. The spectroscopy was done on molecules purified by HPLC frozen immediately to inhibit isomerization. The spectra were taken at 77 K to maintain the configurations and to provide better spectral resolution than seen at room temperature. The kinetics reveal that for all of the molecules except neoxanthin, the S1 state lifetime of the cis isomers is shorter than that of the all-trans isomers. The S1 excited state energies of all the isomers were determined by recording S1 → S2 transient absorption spectra. The results obtained in this manner at cryogenic temperatures provide an unprecedented level of precision in the measurement of the S1 energies of these xanthophylls, which are critical components in light-harvesting pigment-protein complexes of green plants.