Femtosecond Time-Resolved Stimulated Raman Spectroscopy: Application to the Ultrafast Internal Conversion in β-Carotene

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Abstract
We have developed the technique of femtosecond stimulated Raman spectroscopy (FSRS), which allows the rapid collection of high-resolution vibrational spectra on the femtosecond time scale. FSRS combines a sub-50 fs actinic pump pulse with a two-pulse stimulated Raman probe to obtain vibrational spectra whose frequency resolution limits are uncoupled from the time resolution. This allows the acquisition of spectra with -1 frequency resolution. Additionally, FSRS is unaffected by background fluorescence, provides rapid (100 ms) acquisition times, and exhibits traditional spontaneous Raman line shapes. FSRS is used here to study the relaxation dynamics of β-carotene. Following optical excitation to S2 (1Bu+) the molecule relaxes in 160 fs to S1 (2Ag-) and then undergoes two distinct stages of intramolecular vibrational energy redistribution (IVR) with 200 and 450 fs time constants. These processes are attributed to rapid (200 fs) distribution of the internal conversion energy from the S1 CC modes into a restricted bath of anharmonically coupled modes followed by complete IVR in 450 fs. FSRS is a valuable new technique for studying the vibrational structure of chemical reaction intermediates and transition states.

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