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 S1 state modes are enhanced by a factor of approximately 200 compared with 800 nm FSRS experiments. The improved signal-to-noise ratios facilitate the measurement of definitive time constants for beta-carotene dynamics including the 180 fs appearance of the S1 vibrational features due to direct internal conversion from S2 and their characteristic 9 ps decay to S0. By tuning the FSRS system to 590 nm Raman excitation, we are able to selectively enhance vibrational features of the hot ground state S hot 0 and monitor its approximately 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.
Shim
Sangdeok
S
Department of Chemistry, University of California, Berkeley, California 94720, USA.
Mathies
Richard A
RA
D012015:Reference Standards; D013059:Spectrum Analysis, Raman / Q000295:instrumentation* / Q000379:methods* / Q000592:standards; D013237:Stereoisomerism; D013997:Time Factors; D019207:beta Carotene / Q000737:chemistry*
D019207:beta Carotene