Broadband pump-probe spectroscopy with sub-10-fs resolution for probing ultrafast internal conversion and coherent phonons in carotenoids

"We use pump-probe spectroscopy with broadband detection to study electronic energy relaxation and coherent vibrational dynamics in carotenoids. A fast optical multichannel analyzer combined with a non-collinear optical parametric amplifier allows simultaneous acquisition of the differential transmission dynamics on the 500-700 nm wavelength range with sub-10-fs temporal resolution. The broad spectral coverage enables on the one hand a detailed study of the ultrafast bright-to-dark state internal conversion process; on the other hand, the tracking of the motion of the vibrational wavepacket launched on the ground state multidimensional potential energy surface. We present results on all-trans P-carotene and on a long-chain polyene in solution. The developed experimental setup enables the straightforward acquisition and analysis of coherent vibrational dynamics, highlighting time-frequency domain features with extreme resolution. (C) 2008 Elsevier B.V. All rights reserved."