Journal of Physical Chemistry B, Vol.112, No.15, 4826-4832, 2008
Development of a tunable femtosecond stimulated Raman apparatus and its application to beta-carotene
We have developed a tunable femtosecond stimulated Raman spectroscopy (FSRS) apparatus and used it to perform time-resolved resonance Raman experiments with < 100 fs temporal and < 35 cm(-1) spectral resolution. The key technical change that facilitates this advance is the use of a tunable narrow-bandwidth optical parametric amplifier (NB-OPA) presented recently by Shim et al. (Shim, S.; Mathies, R. A. Appl. Phys. Lett. 2006, 89, 121124). The practicality of tunable FSRS is demonstrated by examining the photophysical dynamics of beta-carotene. Using 560 nm Raman excitation, the resonant S-1 state modes are enhanced by a factor of similar to 200 compared with 800 nm FSRS experiments. The improved signal-to-noise ratios facilitate the measurement of definitive time constants for P-carotene dynamics including the 180 fs appearance of the S-1 vibrational features due to direct internal conversion from S-2 and their characteristic 9 ps decay to S-0. By tuning the FSRS system to 590 nm Raman excitation, we are able to selectively enhance vibrational features of the hot ground state (S-0(hot)) and monitor its similar to 5 ps cooling dynamics. This tunable FSRS system is valuable because it facilitates the direct observation of structural changes of selected resonantly enhanced states and intermediates during photochemical and photobiological reactions.