Electronic resonances in broadband stimulated Raman spectroscopy.

Spontaneous Raman spectroscopy is a formidable tool to probe molecular vibrations. Under electronic resonance conditions, the cross section can be selectively enhanced enabling structural sensitivity to specific chromophores and reaction centers. The addition of an ultrashort, broadband femtosecond pulse to the excitation field allows for coherent stimulation of diverse molecular vibrations. Within such a scheme, vibrational spectra are engraved onto a highly directional field, and can be heterodyne detected overwhelming fluorescence and other incoherent signals. At variance with spontaneous resonance Raman, however, interpreting the spectral information is not straightforward, due to the manifold of field interactions concurring to the third order nonlinear response. Taking as an example vibrational spectra of heme proteins excited in the Soret band, we introduce a general approach to extract the stimulated Raman excitation profiles from complex spectral lineshapes. Specifically, by a quantum treatment of the matter through density matrix description of the third order nonlinear polarization, we identify the contributions which generate the Raman bands, by taking into account for the cross section of each process.

Energy flow between spectral components in 2D broadband stimulated Raman spectroscopy.

We introduce a general theoretical description of non resonant impulsive femtosecond stimulated Raman spectroscopy in a multimode harmonic model. In this technique an ultrashort actinic pulse creates coherences of low frequency modes and is followed by a paired narrowband Raman pulse and a broadband probe pulse. Using closed-time-path-loop (CTPL) diagrams, the response on both the red and the blue sides of the broadband pulse with respect to the narrowband Raman pulse is calculated, the process couples high and low frequency modes, which share the same ground state. The transmitted intensity oscillates between the red and the blue side, while the total number of photons is conserved. The total energy of the probe signal is periodically modulated in time by the coherence created in the low frequency modes.