The concurrent dynamics of the electronic excitation and vibronic oscillations of spheroidene have been investigated by means of the transient grating (TG) spectroscopy. The third-order optical responses of spheroidene in an organic solvent, in the LH2 light-harvesting antenna complexes, and in chromatophores have been compared in order to investigate the influence of the environment surrounding this photosynthetic pigment. Vibronic coherent oscillations with a period of several tens of femtosecond have been clearly observed superimposed on a slowly varying background, which reflects the electronic dynamics. The dynamics of the coherent oscillations have been analyzed by means of the wavelet analysis. Within our experimental accuracy, the decay times of the CC and CC stretching modes and CCH3 rocking mode of each specimen are very close. The experimental results have also been analyzed using a Brownian oscillator model. For these numerical calculations, the spectral density for the underdamped modes has been determined from the Raman spectrum of spheroidene. It was found that the low-frequency modes that reflect the influence of the protein environment can be approximated by the overdamped Brownian oscillator. The experimentally observed linear absorption spectra as well as the third-order optical responses, i.e., TG curves, are reproduced very well by these calculations. The close agreement between the experiments and calculations indicates that the Feynman-diagrammatic approach can be applied to express not only the internal conversion but also the intermolecular excitation energy-transfer processes. The vibronic decay rates of spheroidene in LH2 complexes and chromatophores are evaluated to be about 20% larger than in the organic solvent.
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