Quantum theory of time-resolved femtosecond stimulated Raman spectroscopy: direct versus cascade processes and application to CDCl3

We present a quantum mechanical wave packet treatment of time-resolved femtosecond stimulated Raman spectroscopy (FSRS), or two-dimensional (2D) FSRS, where a vibrational coherence is initiated with an impulsive Raman pump which is subsequently probed by FSRS. It complements the recent classical treatment by Mehlenbacher et al. [J. Chem. Phys. 131, 244512 (2009)]. In this 2D-FSRS, two processes can occur concurrently but with different intensities: a direct fifth-order process taking place on one molecule, and a cascade process comprising two third-order processes on two different molecules. The cascade process comprises a parallel and a sequential cascade. The theory is applied to the 2D-FSRS of CDCl(3) where calculations showed that: (a) the cascade process is stronger than the direct fifth-order process by one order of magnitude, (b) the sidebands assigned to C-Cl E and A(1) bends, observed on both sides of the Stokes C-D stretch frequency, are not due to anharmonic coupling between the C-D stretch and the C-Cl bends, but are instead due to the coherent anti-Stokes Raman spectroscopy (CARS) and coherent Stokes Raman spectroscopy (CSRS) fields produced in the first step of the cascade process, (c) for each delay time between the femtosecond impulsive pump and FSRS probe pulses, the line shape of the sidebands shows an inversion symmetry about the C-D stretch frequency, and this is due to the 180(°) phase difference between the CARS and CSRS fields that produced the left and right sidebands, and (d) for each sideband, the line shape changes from positive Lorentzian to dispersive to negative Lorentzian, then to negative dispersive and back to positive Lorentzian with the period of the bending vibration, and it is correlated with the momentum of the wave packet prepared on the ground-state surface by the impulsive pump along the sideband normal coordinate.