We use a 6.8-fs laser as the light source for broad-band femtosecond pump-probe real-time vibrational spectroscopy to investigate both electronic relaxation and vibrational dynamics of the Q(y)-band of Chl-a at 293 K. More than 25 vibrational modes coupled to the Q(y) transition are observed. Eleven of them have been clarified predominantly due to the excited state, and six of them are concluded to be nearly exclusively resulting from the ground-state wave-packet motion. Moreover, thanks to the broad-band detection over 5000 cm⁻¹, the modulated signals due to the excited state vibrational coherence are observed on both sides of the 0-0 transition with equal separation. The corresponding nonlinear process has been studied using a three-level model, from which the probe wavelength dependence of the phase of the periodic modulation can be calculated. The probe wavelength dependence of the vibrational amplitude is interpreted in terms of the interaction between the "pump" or "laser," Stokes, and anti-Stokes field intermediated by the molecular vibrations. In addition, an excited state absorption peak at ~709 nm has been observed. To the best of our knowledge, this is the first study of broad-band real-time vibrational spectroscopy in Chl-a.

Real-time impulsive resonant Raman scattering induced by a 4-fs ultrashort laser pulse was spectrally resolved with a multichannel lock-in amplifier. An optical and vibrational two-dimensional spectrum was introduced to separate the effects of electronic and vibrational broadening in the power spectrum of the vibrations. Spectrally resolved real-time oscillations can identify the wave packet motion associated with the stretching vibrational mode of the carbon-carbon double and triple bonds of the polymer polydiacetylene. Calculated nonlinear polarizations which take into account the ground-state wave packets reproduced the observed dynamics fairly well. It is confirmed that the ground-state vibrations play a significant role in the dynamics of the wave packet even far below the absorption edge, as well as the excited-state vibrations.

We present the principles, experimental procedures, applications, and theoretical analyses of femtosecond phase spectroscopy, which is complementary to femtosecond absorption spectroscopy. In femtosecond phase spectroscopy difference spectra of both phase and transmission are simultaneously measured with a frequency-domain interferometer, which is only slightly modified from the conventional pump-probe method. Femtosecond time-resolved dispersion relations for CdS x Se 12x-doped glass and CS 2 are obtained with transform-limited pulses of 60-fs duration and 620-nm center wavelength. The results are theoretically analyzed and are well reproduced by numerical simulations. Although time-resolved data are not expected to satisfy the Kramers-Kronig (K-K) relations, the degree of discrepancy from the K-K relations is more substantial for CS 2 than for CdS x Se 12x-doped glass. These results arise from the difference in the linear susceptibility and in the excited-population dynamics. The conditions for which the K-K relations are applicable to time-resolved spectra are obtained theoretically and verified experimentally. It is shown that induced amplitude and phase modulations of the probe pulses cause a deviation from the K-K relations.

We report the development of a multiplex stimulated Raman microscope for spectral imaging through multi-channel lock-in detection with a single light source. A white pump beam is prepared with a piece of photonic crystal fiber (PCF). The system does not require the synchronization of plural light sources or the scanning of their wavelengths, and thus a jitter-free pair of pump and Stokes beams is obtained, and a high degree of temporal synchronization is attained in the spectra. The multi-channel lock-in detection (extended to 128 channels) enables the observation of pseudo-continuous stimulated Raman spectra, demonstrating the strong ability of qualitative analysis to identify various types of C-H stretching modes such as the symmetric and asymmetric modes of the methylene∕methyl and aromatic groups. Images of a mixed film of polystyrene and polymethylmethacrylate are presented to demonstrate the system's spectral imaging ability. The spatial distribution of these materials is successfully captured through one-time imaging, although the noise of the white light pump beam generated with the PCF limits the system's imaging speed.