Rotational CARS N2 thermometry: validation experiments for the influence of nitrogen spectral line broadening by hydrogen

Rotational coherent anti‐Stokes Raman spectroscopy (CARS) in fuel‐rich hydrocarbon flames, with a large content of hydrogen in the product gases (∼20%), has in previous work shown that evaluated temperatures are raised several tens of Kelvin by taking newly derived N₂ H₂ Raman line widths into account. To validate these results, in this work calibrated temperature measurements at around 300, 500 and 700 K were performed in a cell with binary gas mixtures of nitrogen and hydrogen. The temperature evaluation was made with respect to Raman line widths either from self‐broadened nitrogen only, N₂ N₂ [energy‐corrected‐sudden (ECS)], or by also taking nitrogen broadened by hydrogen, N₂ H₂ [Robert–Bonamy (RB)], Raman line widths into account. With increased amount of hydrogen in the cell at constant temperature, the evaluated CARS temperatures were clearly lowered with the use of Raman line widths from self‐broadened nitrogen only, and the case with inclusion of N₂ H₂ Raman line widths was more successful. The difference in evaluated temperatures between the two different sets increases approximately linearly, reaching 20 K (at T ∼ 300 K), 43 K (at T = 500 K) and 61 K (at T = 700 K) at the highest hydrogen concentration (90%). The results from this work further emphasize the importance of using adequate Raman line widths for accurate rotational CARS thermometry. Copyright © 2010 John Wiley & Sons, Ltd.     

CARS thermometry revisited in lightof the intramolecular perturbation

The rigid rotor approximation (RRA) is commonly assumed in the Raman cross section used in thermometric analysis based on coherent anti‐Stokes Raman scattering (CARS). In this paper, we discuss instead the role of the coupling between molecular vibrations and rotations in view of the alterations found in the amplitude of CARS signals of basic molecules and, in the end, we demonstrate that the deviation of a few percent from the RRA results in corrections to the measured temperature that are comparable to the thermometric accuracy of very well‐known Q‐branch CARS measurements on nitrogen, which is unanimously regarded as the fundamental molecule in CARS thermometry. Copyright © 2010 John Wiley & Sons, Ltd.     

Aspects of hydrogen CARS thermometry

The temperature of hydrogen in a graphite tube furnace has been determined using broadband coherent anti-Stokes Raman scattering (CARS) spectroscopy. Significant laser-induced population changes were observed within the vibrational state manifold, whereas the rotational envelope in both fundamental and hot band remained unchanged.     

激发态H2(X1∑+g,v=1,J=1)之间的碰撞能量合并

受激拉曼激发H2(0,1)基态的Q支得到H2(1,1)能级.在室温条件下,利用反斯托克斯拉曼散射(CARS)探测技术测量了碰撞能量合并(EP)过程H2(1,1)+H2(1,1)→H2(2,J)+H2(0,J″)及H2(1,1)与H2(1,J)转动能级间的碰撞转移速率系数.扫描CARS谱表明在H2(1,1)能级的碰撞能量...     

CARS temperature measurement in a LOX/CH4 spray flame

Coherent anti‐Stokes Raman scattering (CARS) spectroscopy has been used to investigate cryogenic liquid oxygen/gaseous methane (LOX/CH₄) flames on a medium‐size test facility at a pressure of 0.24 MPa and mass flow of 0.025 kg/s. Single‐shot, broadband CARS spectra with simultaneous detection of the Q‐branches of hydrogen and water molecules were recorded with good signal‐to‐noise ratio. Temperature was deduced from the H₂ and H₂O CARS profiles. The spatial temperature distribution in a comparatively harsh environment has been measured successfully. The measurements took place in the windowed combustion chamber of the DLR M3 test facility, aiming to provide data for validation of rocket combustor modeling. Copyright © 2010 John Wiley & Sons, Ltd.     

Mitigating heat dissipation in Raman lasers using coherent anti-stokes Raman scattering

We present a novel technique that intrinsically mitigates the quantum-defect heating in Raman lasers. The basic principle of this so-called "coherent anti-Stokes Raman scattering (CARS)-based heat mitigation" is to suppress the phonon creation in the Raman medium by increasing the number of out-coupled anti-Stokes photons with respect to the number of out-coupled Stokes photons. We demonstrate with the aid of numerical simulations that for a hydrogen and a silicon Raman laser, CARS-based heat mitigation efficiencies of at least 30% and 35%, respectively, can be obtained.     

Hydrogen CARS thermometry in H2–N2 mixtures at high pressure and medium temperatures: influence of linewidths models

In order to improve the accuracy of H₂ CARS thermometry, H₂ Q-branch CARS spectra have been recorded for various H₂-N₂ mixtures in a high-pressure cell at different pressures and temperatures (up to 40 bar and 875 K). Due to the low spectral resolution of broadband CARS experiments, the relevant spectral lineshape factor is the linewidth ratio &(Q(3))/&(Q(1)), since Q(1) and Q(3) are the most intense lines of the Q-branch spectrum in this temperature range. For the first time, the speed-inhomogeneous effects are accounted for in the simulation of the CARS profiles. The evaluated temperatures are in good agreement with reference values obtained by thermocouples. The specific role on the accuracy of H₂ CARS thermometry of the speed inhomogeneity is carefully analyzed, in connection with the influence of the nitrogen concentration.     

Coherent anti‐Stokes Raman scattering in Raman lasers and Raman wavelength converters

In this paper recent research progress on the use of Coherent Anti‐Stokes Raman Scattering (CARS) in Raman lasers and Raman wavelength converters is reviewed. The latest insights in the physical nature and behavior of CARS are addressed, and the recent performance breakthroughs in CARS‐based Raman wavelength conversion are discussed. Based on the new findings regarding the behavior of CARS, a physical explanation for apparent inconsistencies in various experimental observations of Raman wavelength conversion is provided. To conclude it is shown that these recent insights also pave the way to the development of a novel CARS‐based mechanism for reducing the heat dissipation in Raman lasers.     

CARS diagnostics of fluid adsorption and condensation in small mesopores

Coherent anti‐Stokes Raman scattering (CARS) spectroscopy is applied to diagnostics of phase behavior of a fluid in pores of nanoporous glasses. Samples with mean pore radii of 2 and 3.5 nm were filled with compressed carbon dioxide at near‐room temperatures. CARS spectra of the 1388 cm⁻¹ Q‐branch were measured at isothermal compressing in a wide pressure range including the transition from gaseous to condensed state. The spectra show specific transformations caused by fluid adsorption and condensation in nanopores. We have carried out calculations of the spectral profiles based on the phase behavior of carbon dioxide in cylindrical glass nanopores. Phase behavior modeling was performed using thermodynamic concepts of surface adsorption and capillary condensation. A good agreement between experimental spectra and calculations was obtained. The potential of CARS technique for the diagnostics of fluid phase behavior in pores and for the characterization of nanoporous host structure is discussed. Copyright © 2011 John Wiley & Sons, Ltd.     

Comparison of the Raman detection limit for IRS- and CARS-spectroscopy at excitation near molecular one-photon resonance

The nonlinear Raman methods IRS and CARS are compared according to the signal detectability at excitation of molecules under the condition of one-photon resonance. At one photon resonance it is the background contribution resulting from the scattering molecules themselves that determines the maximum attainable signal to noise ratio. These contributions acting for IRS and CARS respectively are compared. The essential difference between IRS and CARS results from a 3rd order saturation contribution to IRS, which may mask the IRS Raman signal near exact resonance while it does not contribute to CARS. This gives to CARS the preference before IRS at resonance excitation. The situation for IRS with respect to background is similar to that of spontaneous Raman scattering, where the resonance fluorescence — corresponding to the saturation contribution at IRS — masks the resonance Raman signal.     

Background-free cars studies of carbon monoxide in a flame

Background-free coherent anti-Stokes Raman spectra (CARS) of carbon monoxide have been obtained in a rich methane-air flat flame. Use of this background rejection method, requiring only two laser frequencies, results in an increase in signal-to-noise of over 200 in the |x⁽³⁾|² spectrum in comparison with normal CARS. In addition, this technique provides a means for determining the symmetry of observed Raman transitions. The principles of background-free CARS are derived, and the capabilities are demonstrated with experimental data.     

Hyper Raman spectra calculated in a time-dependent Hartree–Fock method

Hyper Raman scattering (HRS) of the benzonitrile (BN) and 1,3,5-trinitro-1,3,5-triazacyclohexane (RDX) molecules is studied by means of ab initio calculations. The computational procedure employs a recently developed methodology for the analytic calculations of frequency-dependent polarizability gradients of arbitrary order, including perturbation dependent basis sets. The result are compared to normal Raman scattering (NRS) and coherent anti-Stokes Raman scattering (CARS) that previously have been studied using the same technology. It is found that some suppressed or silent modes in CARS and NRS spectra are clearly seen in HRS, and that although under general excitation conditions the HRS intensities are much lower than for CARS and NRS, HRS provides complementary information useful for target identification.     

基于光强传输方程相位成像的宽场相干反斯托克斯拉曼散射显微背景抑制

相干反斯托克斯拉曼散射(CARS)显微能够对样品的特殊化学组分进行选择性成像,无需荧光标记,在生物医学领域被广泛应用.然而,传统的CARS图像往往存在非共振背景信号.本文将基于光强传输方程的单光束相位成像技术用于CARS显微成像,来抑制CARS的非共振背景信号.该方法通过记录样品在三个相邻平面上的CARS图像,然后利用光强传输方程获取CARS光场的相位分布,最后利用共振CARS信号和非共振背景信号在相位上的差异,实现了对背景噪声的抑制.该方法无需参考光,通过三次测量可完成CARS的背景噪声抑制,具有良好的应用前景.     

Selective excitation and suppression of coherent anti-Stokes Raman scattering by shaping femtosecond pulses

Femtosecond coherent anti-Stokes Raman scattering (CARS) suffers from poor selectivity between neighbouring Raman levels due to the large bandwidth of the femtosecond pulses. This paper provides a new method to realize the selective excitation and suppression of femtosecond CARS by manipulating both the probe and pump (or Stokes) spectra. These theoretical results indicate that the CARS signals between neighbouring Raman levels are differentiated from their indistinguishable femtosecond CARS spectra by tailoring the probe spectrum, and then their selective excitation and suppression can be realized by supplementally manipulating the pump (or Stokes) spectrum with the $\pi $ spectral phase step.     

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.     

Shot-by-shot frequency calibration of CARS spectra: Application to the measurement of the collisional line shift in oxygen

A technique using a Fabry-Perot interferometer has been developed to calibrate high-resolution spectra obtained by Coherent Anti-Stokes Raman Spectroscopy (CARS). This technique was used to measure simultaneously the Raman frequency and the Raman signal at each laser shot. We demonstrate the accuracy of the method by measuring theQ(15) line shifts of molecular oxygen due to collisions with oxygen and water vapour.     

Single-pulse CARS spectra in solid propellant combustion at atmosphere pressure

The unstable-resonator spatially enhanced detection (USED) coherent anti-stokes Raman spectroscopy (CARS) measurements of temperature and N2 concentration in the combustion of solid propellant at atmosphere pressure are reported. The USED CARS measurement system has a high spatial solution of ~ 0.1 mm in diameter and 3 mm in length, and permits instantaneous measurement at 10-Hz rate. The single-pulse N2 Q-branch CARS spectra have been obtained from the propellant combustion. The temperatures and N2 concentrations of the propellant flame at different height have been achieved by fitting the experimental data to theoretical spectra. The results indicate that the temperature is up to ~ 2500 K with N2 concentration in a range from 10% to 26%.     

Coherent anti-Stokes Raman scattering of slow light in a hollow planar periodically corrugated waveguide

Enhancement of coherent anti-Stokes Raman scattering (CARS) by molecular nitrogen in a hollow planar periodically corrugated waveguide is experimentally detected. The measured dependence of CARS efficiency on the thickness of the waveguide layer indicates that CARS enhancement under these conditions is at least partially due to the decrease in the group velocity of pump pulses around the photonic band gap.     

Coherent anti-Stokes Raman scattering and normal anti-Stokes Raman scattering due to LO phonons in GaP using cw diode lasers

Coherent anti-Stokes Raman scattering (CARS) and normal anti-Stokes Raman scattering (NARS) have been measured in (001) GaP at room temperature due to the 403 cm⁻¹ LO phonons using a continuous wave (CW) 785.0 nm fixed-wavelength pump laser and a CW Stokes laser tunable in the 800-830 nm wavelength range. CARS measurements are normally made using pulsed lasers. The use of CW diode lasers allows a more accurate comparison between the measured and calculated values of the CARS signal. The pump and Stokes laser beams were linearly polarized perpendicular to each other, same as the pump and normal Stokes/anti-Stokes scattered light for the GaP sample used in this work. The pump and Stokes laser powers incident upon the GaP sample, located in the focal plane of a 20 mm effective focal length lens, were <20 and 50 mW, respectively. The diameter of the laser beams in the focal plane of the focusing lens was determined to 40±5 μm. The pump and Stokes laser beam intensities incident upon the 0.3 mm thick GaP sample were <2 and 5 kW cm², respectively. The powers of the CARS and NARS signals were measured using a Raman spectrometer. The signal output of the Raman spectrometer was calibrated using the pump laser and several neutral density filters. The Raman linewidth (full-width at half-maximum) of the LO phonons was determined to be 0.95±0.05 cm⁻¹, using the variation of the CARS signal with the wavelength of the Stokes laser. The measured powers of the CARS and NARS signals are about a factor of 5 and 1.5, respectively, smaller than those calculated from the corresponding theoretical expressions.     

The line shape of Coherent Antistokes Raman Scattering excited under resonance conditions

If Coherent Antistokes Raman Scattering (CARS) is excited by a biharmonic pump in resonance with one photon molecular transition, the Raman line shape is significantly changed compared to the case of nonresonant excitation. This is due to an essential alteration of the 3rd order susceptibility responsible for CARS. Aside from a considerable enhancement of the Raman signal (which makes it possible to detect dissolved molecules in concentration lower than 10^-4 mole/l) the most marked effects are a reversal of the spectral sequence of the Raman maximum and minimum in the CARS-spectrum and for a specially chosen concentration an enhanced contrast of the signal. The factors determining the CARS line shape are discussed theoretically and preliminary experimental results concerning resonance CARS spectra are reported.