Coherent oscillations in ultrafast fluorescence of photoactive yellow protein

• Published in: The Journal of chemical physics Vol. 127; no. 21; p. 215102
• Main Authors: Nakamura, Ryosuke, Hamada, Norio, Ichida, Hideki, Tokunaga, Fumio, Kanematsu, Yasuo
• Format: Journal Article
• Language: English
• Published: United States 07.12.2007
• Subjects: Bacterial Proteins - chemistry; Bacterial Proteins - radiation effects; Light; Models, Chemical; Photochemistry; Photoreceptors, Microbial - chemistry; Photoreceptors, Microbial - radiation effects; Spectrometry, Fluorescence
• ISSN: 0021-9606
• DOI: 10.1063/1.2802297

The ultrafast photoinduced dynamics of photoactive yellow protein in aqueous solution were studied at room temperature by femtosecond fluorescence spectroscopy using an optical Kerr-gate technique. Coherent oscillations of the wave packet were directly observed in the two-dimensional time-energy map of ultrafast fluorescence with 180 fs time resolution and 5 nm spectral resolution. The two-dimensional map revealed that four or more oscillatory components exist within the broad bandwidth of the fluorescence spectrum, each of which is restricted in the respective narrow spectral region. Typical frequencies of the oscillatory modes are 50 and 120 cm(-1). In the landscape on the map, the oscillatory components were recognized as the ridges which were winding and descending with time. The amplitude of the oscillatory and winding behaviors is a few hundred cm(-1), which is the same order as the frequencies of the oscillations. The mean spectral positions of the oscillatory components in the two-dimensional map are well explained by considering the vibrational energies of intramolecular modes in the electronic ground state of the chromophore. The entire view of the wave packet oscillations and broadening in the electronic excited state, accompanied by fluorescence transitions to the vibrational sublevels belonging to the electronic ground state, was obtained.