Search for: All records

Generating wavelength-tunable picosecond laser pulses from an ultrafast laser source is essential for femtosecond stimulated Raman scattering (FSRS) measurements. Etalon filters produce narrowband (picosecond) pulses with an asymmetric temporal profile that is ideal for stimulated resonance Raman excitation. However, direct spectral filtering of femtosecond laser pulses is typically limited to the laser’s fundamental and harmonic frequencies due to very low transmission of broad bandwidth pulses through an etalon. Here, we show that a single etalon filter (15 cm−1 bandwidth; 172 cm−1 free spectral range) provides an efficient and tunable option for generating Raman pump pulses over a wide range of wavelengths when used in combination with an optical parametric amplifier and a second harmonic generation (SHG) crystal that has an appropriate phase-matching bandwidth for partial spectral compression before the etalon. Tuning the SHG wavelength to match individual transmission lines of the etalon filter gives asymmetric picosecond pump pulses over a range of 460–650 nm. Importantly, the SHG crystal length determines the temporal rise time of the filtered pulse, which is an important property for reducing background and increasing Raman signals compared with symmetric pulses having the same total energy. We examine the wavelength-dependent trade-off between spectral narrowing via SHG and the asymmetric pulse shape after transmission through the etalon. This approach provides a relatively simple and efficient method to generate tunable pump pulses with the optimum temporal profile for resonance-enhanced FSRS measurements across the visible region of the spectrum. 

Some diarylethene molecular switches have a low quantum yield for cycloreversion when excited by a single photon, but react more efficiently following sequential two-photon excitation. The increase in reaction efficiency depends on both the relative time delay and the wavelength of the second photon. This paper examines the wavelength-dependent mechanism for sequential excitation using excited-state resonance Raman spectroscopy to probe the ultrafast (sub-30 fs) dynamics on the upper electronic state following secondary excitation. The approach uses femtosecond stimulated Raman scattering (FSRS) to measure the time-gated, excited-state resonance Raman spectrum in resonance with two different excited-state absorption bands. The relative intensities of the Raman bands reveal the initial dynamics in the higher-lying states, Sn, by providing information on the relative gradients of the potential energy surfaces that are accessed via secondary excitation. The excited-state resonance Raman spectra reveal specific modes that become enhanced depending on the Raman excitation wavelength, 750 or 400 nm. Many of the modes that become enhanced in the 750 nm FSRS spectrum are assigned as vibrational motions localized on the central cyclohexadiene ring. Many of the modes that become enhanced in the 400 nm FSRS spectrum are assigned as motions along the conjugated backbone and peripheral phenyl rings. These observations are consistent with earlier measurements that showed higher efficiency following secondary excitation into the lower excited-state absorption band and illustrate a powerful new way to probe the ultrafast dynamics of higher-lying excited states immediately following sequential two-photon excitation.