Broadband (1000 cm−1) multiplex CARS spectroscopy: Application to polarization sensitive and time-resolved measurements

A multiplex CARS spectrometer based on a cw diode-pumpedQ-switched Nd: YLF laser, a broadband dye-laser and a multichannel spectrum detection system has been constructed. Excellent mode characteristics of the laser beams and high pulse repetition rate (2 kHz) have resulted in good signal-to-noise ratio achieved with a few seconds accumulation time. A 1000 cm^–1 wide spectral range is covered in a single CARS spectrum with an expanded bandwidth of the dye laser. A thin-jet sampling method is used in order to avoid the phase-matching limitation. The efficient spectral intensity normalization by the reference (CCl₄) nonresonant spectrum and subsequent computer fitting have been implemented. The performance of the system is demonstrated by two different experiments. First, the polarization sensitive measurements (PS-CARS) of cyclohexane show its potential for accurate Raman depolarization ratio determination and for detection of weak (overlapped) Raman bands. Second, the transient resonance CARS measurement of the lowest excited triplet state of all-trans retinal indicate its feasibility to time-resolved CARS spectroscopy of fluorescent excited states.