Background-free coherent Raman spectroscopy by detecting the spectral phase of molecular vibrations

We propose and demonstrate a new approach to subtracting high nonresonant background in coherent anti-Stokes Raman scattering spectroscopy. The method is based on the retrieval of the spectral phase of molecular vibrations using the technique of frequency-resolved optical gating of Raman scattering. In the presence of high nonresonant background the retrieved phase corresponds directly to the background-free spectrum of the coherent Raman response.     

Single-pulse phase-contrast nonlinear Raman spectroscopy

High spectral resolution nonlinear vibrational spectroscopy with a single ultrashort pulse is demonstrated on a variety of samples. The spectral data are obtained by shaping the excitation pulse in order to control the relative phase between the weak resonant signal and the strong nonresonant background, in analogy with phase-contrast microscopy techniques. This is unlike the more conventional approach to nonlinear spectroscopy, in which the nonresonant background is reduced to a minimum. By measuring the spectrum of the coherent anti-Stokes Raman signal, it is possible to infer the vibrational energy levels in a band spanning almost an entire octave.     

Polarization coherent anti-Stokes Raman scattering microscopy

We report polarization coherent anti-Stokes Raman scattering (P-CARS) microscopy that allows vibrational imaging with high sensitivity and spectral selectivity. The nonresonant background signals from both Raman scatterers and the solvent are efficiently suppressed in P-CARS microscopy. We demonstrate P-CARS imaging of unstained cells based on the contrast of the protein amide I band.     

Time‐resolved coherent anti‐Stokes Raman spectroscopy impulsively excited by supercontinuum

Time‐resolved coherent anti‐Stokes Raman scattering (CARS) impulsively excited by a supercontinuum (SC) is investigated. We show that it is critical to optimize the temporal overlapping of the constituent solitons of a SC in order to impulsively excite vibrational modes over a broad frequency range. The cross‐correlation frequency‐resolved optical gating technique is utilized to retrieve the optical response function of molecules under SC impulsive excitation, and background‐free CARS with spectral resolution significantly better than the bandwidth of the probe pulses is achieved. Copyright © 2011 John Wiley & Sons, Ltd.     

Characterization of a supercontinuum generated from a photonic crystal fiber and its application to coherent Raman spectroscopy

The temporal and spectral profiles of supercontinuum radiation generated from a photonic crystal fiber are evaluated with a polarization-gate frequency-resolved optical gating technique. The supercontinuum is then applied to coherent inverse Raman spectroscopy. A stimulated Raman signal of cyclohexane is observed as an induced absorption signal with an instantaneous response. The Raman signal has a peak at a slight negative delay time, which is explained by perturbed Raman-induced coherence.     

Coherent anti-stokes raman scattering spectral interferometry: determination of the real and imaginary components of nonlinear susceptibility chi(3) for vibrational microscopy

We demonstrate coherent anti-Stokes Raman scattering (CARS) heterodyne spectral interferometry for retrieval of the real and imaginary components of the third-order nonlinear susceptibility (chi(3)) of molecular vibrations. Extraction of the imaginary component of chi(3) allows a straightforward reconstruction of the vibrationally resonant signal that is completely free of the electronic nonresonant background and resembles the spontaneous Raman spectrum. Heterodyne detection offers potential for signal amplification and enhanced sensitivity for CARS microscopy.     

Ultrabroadband background-free coherent anti-Stokes Raman scattering microscopy based on a compact Er:fiber laser system

We demonstrate a scheme for efficient coherent anti-Stokes Raman scattering (CARS) microscopy free of nonresonant background. Our method is based on a compact Er:fiber laser source. Impulsive excitation of molecular resonances is achieved by an 11 fs pulse at 1210 nm. Broadband excitation gives access to molecular resonances from 0 cm(-1) up to 4000 cm(-1). Time-delayed narrowband probing at 775 nm enables sensitive and high-speed spectral detection of the CARS signal free of nonresonant background with a resolution of 10 cm(-1).     

The influence of phase-modulation on femtosecond time-resolved coherent Raman spectroscopy

The influence of phase-modulation on femtosecond time-resolved coherent Raman scattering is investigated theoretically and experimentally. The coherent Raman signal taken as a function of the spectral position shows unexpected temporal oscillations close to time zero. A theoretical analysis of the coherent Raman scattering process indicates that the femtosecond light pulses are amplitude and phase modulated. The pulses are asymmetric in time with more slowly decaying trailing wings. The phase of the pulse amplitude contains quadratic and higher-order contributions.     

Optimally chirped CARS using fiber stretchers

High spectral resolution coherent anti-Stokes Raman scattering (CARS) spectroscopy and microscopy are demonstrated with femtosecond laser systems. We perform optimal chirping in glass fibers and demonstrate a spectral resolution enhancement to better than 26 cm⁻¹, which is limited by the bandwidth of the measured resonances. Considering the convolution with the resonance bandwidth this corresponds to a spectral resolution of approximately 2.5 cm⁻¹, which is an enhancement by a factor of 165 with respect to the use of bandwidth-limited pulses. In microscopic imaging, a water background suppression of 81.5% is achieved.     

Fourier transform spectral interferometric coherent anti-Stokes Raman scattering (FTSI-CARS) spectroscopy

A novel Fourier transform spectral interferometric (FTSI) multiplex coherent anti-Stokes Raman scattering (CARS) technique is developed to extract the vibrational spectrum equivalent to the spontaneous Raman scattering. The conventional FTSI method is modified to use the internal nonresonant CARS signal as a local oscillator to perform spectral interferometry. Utilizing the causality of the coherent vibration (i.e., there should be no signal before the laser excitation), this new FTSI method recovers the entire complex vibrational spectral parameters. We demonstrate this technique with a previously reported single-pulse multiplex CARS method that uses a single phase-controlled broadband ultrafast laser pulse.     

生物分子拉曼散射测定过程中荧光背景的抑制

拉曼共焦技术、表面拉曼增强技术以及降低入射激光强度的方法，被运用于SOD、DNA等生物分子拉曼散身实验中，以抑制其荧光背景，改善光谱质量。     

Time-resolved coherent anti-Stokes Raman scattering with a femtosecond soliton output of a photonic-crystal fiber

We demonstrate time-resolved coherent anti-Stokes Raman scattering (CARS) by using a frequency-tunable femtosecond soliton output of a silica photonic-crystal fiber (PCF) as a Stokes field. This approach allows quantum beats originating from two close Raman modes to be resolved in the time-domain CARS response. The nonresonant CARS background is efficiently suppressed by introducing a delay time between the probe pulse and the pump-Stokes pulse dyad, suggesting a convenient fiber-optic format for the Stokes source in time-resolved CARS and allowing sensitivity improvement in PCF-based CARS spectroscopes and microscopes.     

混合溶液中CARS过程的非共振信号实验研究

相干反斯托克斯拉曼散射是一种非线性四波混频效应,但是通过探测共振信号不易进行物质成分的定量光谱分析。本文利用单频相干反斯托克斯拉曼散射光谱分析法,对不同体积比混合的乙醇溶液在远离双光子共振跃迁及其远离溶质与溶剂的特征拉曼共振态位置进行了光谱探测。通过对实验结果进行分析发现,在共振位置2 876 cm-1的信号强度随混合溶液中的乙醇的体积比增加而增加,呈二次方关系。而在远离共振态位置的非共振信号强度随混合溶液中乙醇的体积比增加而增加,且呈线性关系,进而说明了非共振信号强度随着分子数浓度N呈线性变化关系。因此,通过探测非共振信号强度与分子数浓度关系可以为混合物中特定成分的定量光谱分析提供一种研究途径。     

Pulse-shaper-assisted phase control of a coherent broadband spectrum of Raman sidebands

We report pulse-shaper-assisted phase control of a broad spectrum, aiming to synthesize nonsinusoidal waveforms. We first generate multiple-order coherent Raman sidebands by focusing two laser beams into a piece of diamond. Then we combine five sidebands into a single beam by using a prism. Our setup allows for both coarse, manual phase adjustments and fine tuning of the spectral phases. A flat spectral phase across these five frequency-separated sub-bands is achieved, which implies generation of two to three optical-cycle pulses.     

Simultaneous measurements of global vibrational spectra and dephasing times of molecular vibrational modes by broadband time-resolved coherent anti-Stokes Raman scattering spectrography

In broadband coherent anti-Stokes Raman scattering (CARS) spectroscopy with supercontinuum (SC), the simultaneously detectable spectral coverage is limited by the spectral continuity and the simultaneity of various spectral components of SC in an enough bandwidth. By numerical simulations, the optimal experimental conditions for improving the SC are obtained. The broadband time-resolved CARS spectrography based on the SC with required temporal and spectral distributions is realised. The global molecular vibrational spectrum with well suppressed nonresonant background noise can be obtained in a single measurement. At the same time, the measurements of dephasing times of various molecular vibrational modes can be conveniently achieved from intensities of a sequence of time-resolved CARS signals. It will be more helpful to provide a complete picture of molecular vibrations, and to exhibit a potential to understand not only both the solvent dynamics and the solute-solvent interactions, but also the mechanisms of chemical reactions in the fields of biology, chemistry and material science.     

Heterodyne interferometric polarization coherent anti‐Stokes Raman scattering (HIP‐CARS) spectroscopy

We demonstrate a new technique that combines polarization sensitivity of the coherent anti‐Stokes Raman scattering (CARS) response with heterodyne amplification for background‐free detection of CARS signals. In this heterodyne interferometric polarization CARS (HIP‐CARS), the major drawbacks of polarization and heterodyne CARS are rectified. Using a home‐built picosecond optical parametric oscillator, we are able to address vibrational stretches between 600 and 1650 cm⁻¹ and record continuous high‐resolution Raman equivalent HIP‐CARS spectra. Copyright © 2010 John Wiley & Sons, Ltd.     

Laser-induced gratings in the gas phase excited by Raman-active transitions

We report on a new time-resolved coherent Raman technique that is based on the generation of thermal gratings following a population change among molecular levels that is induced by stimulated Raman pumping. This is achieved by use of spatially and temporally overlapping intensity interference patterns generated independently by two lasers. When this technique is used in carbon dioxide, making use of transitions that belong to the Q branches of the v(1)/2v Fermi dyad, it is possible to investigate molecular energy transfer processes. A further unique feature of this method is spectral resolution that is better than that achieved by coherent anti-Stokes Raman scattering.     

Generation of three-primary-color Raman comb in the continuous-wave regime

We demonstrate the generation of continuous-wave Stokes and anti-Stokes Raman sidebands including the three-primary-color (683, 532, and 436 nm) components. The Raman sidebands are generated through both stimulated and coherent anti-Stokes Raman scattering in a broadband high-finesse optical cavity filled with gas-phase hydrogen as a Raman-active medium and covering the entire visible spectral range (420–680 nm). The blue emission is considerably enhanced by matching the frequency with one of the longitudinal modes of the optical cavity, and high conversion efficiencies are observed when the coherent length corresponds to an integral multiple of the round-trip length of the optical cavity. This indicates that phase-matching plays a critical role in determining the efficiency of the Raman comb generation.     

Pulse shaping by modulation instability in a photonic-crystal fiber for coherence control and single-beam coherent anti-Stokes Raman-scattering microspectroscopy

Modulation instability in a highly nonlinear photonic-crystal fiber is shown to allow the generation of optimally pulse-shaped field waveforms that are ideally suited for coherence-controlled nonlinear Raman scattering, including single-beam coherent anti-Stokes Raman-scattering microspectroscopy. This approach enables the integration of the efficient spectral transformation and pulse-shaping operations needed for the realization of nonlinear Raman techniques in a single fiber-format component.