Femtosecond stimulated Raman spectroscopy

Advances in the field of Femtosecond Stimulated Raman Spectroscopy (FSRS), a new time‐resolved structural technique that provides complete vibrational spectra on the ultrafast timescale, are reviewed. When coupled with a femtosecond optical trigger, the time evolution of a reacting species can be monitored with unprecedented <25 femtosecond temporal and 5 cm^‐1 spectral resolution. New technological and theoretical advances including the development of tunable FSRS and a background‐free FSRS format are discussed. The most recent experimental studies focus on ultrafast reaction dynamics in electronically excited states: isomerization in cyanobacterial phytochrome, ultrafast spin flipping in a solar cell sensitizer, and excited state proton transfer in green fluorescent protein. The use of FSRS to directly map multidimensional reactive potential energy surfaces and to probe the mechanism of reactive internal conversion is prospectively discussed.     

Single-pulse stimulated Raman scattering spectroscopy

We demonstrate the acquisition of stimulated Raman scattering spectra with the use of a single femtosecond pulse. High-resolution vibrational spectra are obtained by shifting the phase of a narrow band of frequencies within the input pulse spectrum, using spectral shaping. The vibrational lines are resolved via amplitude features formed in the spectrum after interaction with the sample. Using this technique, low-frequency Raman lines (<100 cm?1) are observed on both the Stokes and anti-Stokes sides.     

Pump power dependence in resonance femtosecond stimulated Raman spectroscopy

Femtosecond stimulated Raman spectroscopy (FSRS) has emerged as a powerful new technique that is capable of obtaining resonance Raman spectra of fluorescent species and transient photochemical intermediates. Unlike related transient infrared absorption techniques, the FSRS signal is quite sensitive to the laser power utilized in the vibrational probing event. In particular, FSRS spectra are highly sensitive to the intensity of the picosecond Raman‐pump pulse. We have measured the power dependence of the FSRS signal using pulse energies from ~10⁻⁹ to ~10⁻⁵ J and molecules with a range of molar absorptivities at the Raman‐pump wavelength of 400 nm, including β‐carotene (ε₄₀₀ = 58 300 M⁻¹ cm⁻¹), para‐nitroaniline (17 800 M⁻¹ cm⁻¹), nitronaphthalene (247 M⁻¹ cm⁻¹) and ferrocene (57 M⁻¹ cm⁻¹). We show that for strongly absorbing molecular systems, such as β‐carotene and para‐nitroaniline, the ground‐state (GS) FSRS signal actually decreases with increasing pump power at pump fluences above ~10⁻² J cm⁻², due to depletion of the GS population. However, for weakly absorbing species like nitronaphthalene and ferrocene, the signal increases linearly with increasing pump fluence until ~0.5 J cm⁻², at which point two‐photon absorption by the solute induces nonlinear absorption of the pump pulse and attenuation of the FSRS signal. The data are quantitatively simulated with a photophysical kinetic model, and the results are analyzed to provide simple guidelines for acceptable Raman‐pump powers in resonance FSRS experiments. The acceptable Raman‐pump power is proportional to the focused beam area and depends inversely on the sample's molar absorptivity. Copyright © 2013 John Wiley & Sons, Ltd.     

High-resolution stimulated Raman gain spectrum of the ν1 band of SF6

We report rotationally resolved stimulated Raman gain spectra of the ν₁ band of SF₆. The fundamental band exhibits a rigid-rotor type spectrum that is readily fit with a band origin of Δα = 774.5445 and a single rotational term Δβ = ?1.10376 × 10^?4 cm^?1. We also observed and analyzed the ν₁ + ν₆ hotband with band origin at 774.1820 cm^?1. With an experimental resolution of 0.0024 cm^?1 there is no evidence for centrifugal distortion or tensor splitting in either band, although the ν₁ + ν₆ band does exhibit first-order Coriolis splitting as expected.     

A novel demonstration of photoacoustic Raman spectroscopy with combined stimulated Raman pumping in H2 molecule

We present the experimental demonstration of a novel, efficient, and vibrational selective technique to prepare population in vibrational level v″ = 1 using the stimulated Raman pumping. Photoacoustic Raman signal has been studied in non-radiative transitions in the molecule H₂ (v″ = 0) and (v″ = 1). The population fraction in the v″ = 1 level can be estimated by using combined photoacoustic Raman spectroscopy with stimulated Raman pumping for the first time.     

High-resolution inverse Raman spectroscopy of the ν1 band of 28SiH4

A near-Doppler-limited isotropic Raman spectrum of the symmetric stretching fundamental ν₁ of ²⁸SiH₄ has been recorded between 2182.8 and 2187.0 cm^?1 using high-sensitivity “quasi-cw” inverse Raman spectroscopy. The band exhibits compact, nonoverlapping J manifolds, which were measured from Q(0) through Q(13), plus a portion of Q(14). Since ν₁ is in resonance with the nearby infrared-active stretch ν₃, these two bands were analyzed simultaneously using the infrared frequencies of ν₃ reported by Cabana, Gray, Robiette, and Pierre. The results confirm their analysis, in which several perturbation-allowed ν₁ transitions were identified in the infrared, but the molecular constants for the v₁ = 1 state are much better determined with the inclusion of the Raman data. At higher J, ν₁ exhibits significant intensity perturbations due to a breakdown of the selection rule ΔN = 0; these have been quantitatively accounted for.     

Ringdown spectroscopy of stimulated Raman scattering in a whispering gallery mode resonator

We report experimental observations of power-dependent, nonexponential decay of light stored in whispering gallery modes caused by stimulated Raman scattering in the resonator host material. Specifically, we show that the instantaneous decay rate of whispering gallery modes of a calcium fluoride resonator increases as the amount of light stored in the resonator decreases.     

Amorphous to crystalline transformation in Ta2O5 studied by Raman spectroscopy

Many of the interesting properties that make Ta₂O₅ a strategic material for current and future applications in chemistry, microelectronics and optics, depend on its structural characteristics. In this work, we use Raman spectroscopy to probe structural modifications in amorphous Ta₂O₅ coatings submitted to thermal annealing. On the basis of previous knowledge on the crystalline material, we perform Raman spectrum simulations in disordered and partially ordered Ta₂O₅ from a phonon density of states. Calculated spectra are in good agreement with complex experimental spectra. Our original approach allows assignment of the vibrational features of the amorphous material, and quantitative interpretation of observed structural modifications in terms of ordering scales. In addition, it provides numerical indicators to analyse amorphous to crystalline phase transformation. Copyright © 2012 John Wiley & Sons, Ltd.     

Measuring the one-particle excitations of ultracold fermionic atoms by stimulated Raman spectroscopy

We propose a Raman spectroscopy technique which is able to probe the one-particle Green function, the Fermi surface, and the quasiparticles of a gas of strongly interacting ultracold atoms. We give quantitative examples of experimentally accessible spectra. The efficiency of the method is validated by means of simulated images for the case of a usual Fermi liquid as well as for more exotic states: specific signatures of, e.g., a d-wave pseudogap are clearly visible.     

High-resolution gamma-ray spectroscopy

To obtain the highest possible resolution in a measurement has always been one of the major challenges for experimental physicists because increased resolution generally results in progress. At the Institut Laue-Langevin, gamma rays emitted after neutron capture can be recorded with parts-permillion resolution. This is achieved by diffracting the gamma rays on highly perfect Sior Ge crystals. Precise measurement of the Bragg angles and the crystal lattice spacings permits the determination of wavelengths or energies. This outstanding resolving power allows the measurement of extremely small Doppler effects caused by the emission of primary gamma rays. These so-called gamma-ray-induced Doppler broadening measurements have given rise to applications in both nuclear and condensed matter physics.     

Off-resonant fifth-order response function for two-dimensional Raman spectroscopy of liquids CS2 and H2O

The off-resonant fifth-order response functions for two-dimensional (2D) Raman spectroscopy of molecular liquids CS2 and H2O are investigated by using molecular dynamics calculation. This spectroscopy, able to deal with a phase space dynamics, shows the existence of nodal lines in several polarization tensor elements [see L. Kaufman et al., Phys. Rev. Lett. 88, 207402 (2002) for experimental results]. The nodal property is found to arise from the dynamical couplings among rotational modes, not accounted for in a normal mode picture. The effects of anharmonicities and "mode coupling through polarizability" are also investigated by comparing the 2D Raman signal with a constant temperature velocity reassignment echo method.     

High-resolution coherent stokes Raman spectroscopy of theν 1 andν 3 bands of methane

Coherent Stokes Raman spectra of the ν₁ and ν₃ bands of CH₄ have been recorded in mixing two pulsed lasers (ruby and dye) of very good spectral and spatial quality. The results show a resolution of about 0.010 cm⁻¹ for a 10 Torr pressure, corresponding in great part to Doppler broadening.     

Femtosecond stimulated Raman microscopy

A novel type of non-linear Raman microscopy, femtosecond stimulated Raman microscopy (FSRM), is introduced. It employs femtosecond white light pulses and intense picosecond pulses which are derived from a femtosecond laser/amplifier system. The pulses are coupled into a microscope set-up and induce a stimulated Raman process at the focus. The Raman interaction spectrally modulates the white light. These modulations are read-out in multi-channel fashion and allow recording of a complete Raman spectrum of the focal region. By raster-scanning the sample, complete Raman images can be obtained. Raman images of polystyrene beads in water demonstrate the feasibility of the approach. PACS 42.65.Dr; 42.30.Va; 42.65.Re     

High-resolution spectroscopy of CF2Cl2 in a molecular jet

Absorption spectra of CF₂Cl₂ were recorded around 923 cm^–1, with a resolution of 50 MHz. The application of the molecular jet technique considerably simplifies the spectra as compared to room-temperature experiments. Rotational and vibrational temperatures were measured for CF₂Cl₂ pure and seeded in Ar or He. Molecular constants were obtained for thev ₆ vibrational band of the two most abundant chlorine isotopic species, as well as vibrational band origines for thev ₆±v ₄ and thev ₆±v ₅ hot-bands of the CF₂ ³⁵Cl₂ isotope.Guest     

High-resolution Raman spectra with femtosecond pulses: an example of combined time- and frequency-domain spectroscopy

Frequency-domain spectroscopy requires long pulses, whereas time-domain spectroscopy requires short pulses. This Letter demonstrates both theoretically and experimentally that simultaneous detection in frequency and time generates well-resolved spectra using intermediate-length pulses. In the case of coherent Raman spectroscopy, typical femtosecond pulses lie between the time and frequency domains. To demonstrate this method, a high-resolution Raman spectrum of nitrobenzene is obtained from 60 fs pulses. Phase control, pulse shaping, or pulses of widely differing duration are not required.     

High-resolution Raman scattering in oligonucleotides

The high-resolution spectra of short single-stranded oligonucleotides have been measured by the high-sensitivity nonresonant Raman scattering method using the example of the system d(20G, 20T), where G is guanine and T is thymine. The samples under study have been prepared by the chemical synthesis using the solid-phase amidophosphite method on an automatic synthesizer. It has been shown that the spectra observed in the frequency range of 500–1500 cm^?1 can be sufficient for the resolution of spectral components corresponding to vibrations of individual oligonucleotide molecules, which contain a large number of atoms in the unit cell.