CARS in combustion: Prospects and problems

The principles of CARS are reviewed. This technique has achieved important successes in combustion, but its use has been limited mostly to temperature measurements. We demonstrate the feasibility of sensitive single-shot concentration measurements (to 0.2%) with fair accuracy, in spite of the adverse effects of turbulence and saturation. Even better sensitivities will be achieved using electronic resonance enhancement.     

CARS thermometry in high temperature gradients

CARS is an effective non-intrusive technique for measuring gas temperature in combustion environments. In regions of high temperature gradient, however, the CARS signal is complicated by contributions from gas at different temperature. This paper examines theoretically the uncertainty associated with CARS thermometry in steep temperature gradients. In addition, the work compares the temperature predicted from CARS with the adiabatic mixed temperature of the gas resident in the measurement volume. This comparison helps indicate the maximum sample volume size allowed for accurate temperature measurements.     

Broadband (1000 cm−1) multiplex CARS spectroscopy: Application to polarization sensitive and time-resolved measurements

A multiplex CARS spectrometer based on a cw diode-pumpedQ-switched Nd: YLF laser, a broadband dye-laser and a multichannel spectrum detection system has been constructed. Excellent mode characteristics of the laser beams and high pulse repetition rate (2 kHz) have resulted in good signal-to-noise ratio achieved with a few seconds accumulation time. A 1000 cm^–1 wide spectral range is covered in a single CARS spectrum with an expanded bandwidth of the dye laser. A thin-jet sampling method is used in order to avoid the phase-matching limitation. The efficient spectral intensity normalization by the reference (CCl₄) nonresonant spectrum and subsequent computer fitting have been implemented. The performance of the system is demonstrated by two different experiments. First, the polarization sensitive measurements (PS-CARS) of cyclohexane show its potential for accurate Raman depolarization ratio determination and for detection of weak (overlapped) Raman bands. Second, the transient resonance CARS measurement of the lowest excited triplet state of all-trans retinal indicate its feasibility to time-resolved CARS spectroscopy of fluorescent excited states.     

Calculation of the signal time-profile in transient CARS experiments

The expressions for the resonant and non-resonant contributions to the CARS signal in a time-resolved CARS experiment are derived on the basis of a diagrammatic perturbative expansion of the polarization. The laser fields are assumed to be off-resonance with respect to any electronic level of the system. The probe pulse is supposed to be derived from one of the two pump pulses (₁). Under this assumption the effect of the noise content of ₁ laser pulses on the signal time-profile (coherence artefact) is correctly reproduced by modelling the noise as a stationary stochastic process. The choice of appropriate polarization geometries is shown to allow for direct measurement of the individual contributions to the CARS signal; the experiments performed on a KClO₄ single crystal fully confirm the results of the calculation based on our theoretical treatment.     

Achievement of Narrow-Band CARS Signal by Manipulating Broad-band Laser Spectrum

We theoretically demonstrate the achievement of narrow-band coherent anti-Stokes Raman scattering （CARS） signal by manipulating broad-band probe spectrum. The narrowing of the CARS signal depends on the spectrum bandwidth of the probe beam, and thus high-resolution CARS signal for a complicated quantum system can be obtained by the simple spectrum manipulation. Furthermore, the energy-level diagram for the complicated quantum system can also be labelled by measuring the CARS signal at a given frequency.     

The application of single-pulse CARS for temperature measurements in a turbulent stagnation flame

N₂ Q-branch CARS spectra have been recorded and evaluated for temperature determination in a turbulent, premixed CH₄/air stagnation flame with a burner of 40 mm diameter and 22 kW thermal load. Temperature histograms on the flame axis at different distances from the stagnation plate have been measured. Problems of practical applicability are addressed, including those arising from the limited spatial resolution of the BOXCARS geometry, from an insufficient dynamic range of the diode array detector, and from a memory effect of the detector in the case of measurements in highly turbulent flame areas with strong intermittency. Some information is given on the computerized acquisition and on the evaluation of the large amounts of data that are necessary for extensive investigations in large combustion systems.     

Temperature and concentration measurements of molecular hydrogen in a filamentary discharge by coherent anti-stokes raman spectroscopy (CARS)

Coherent anti-Stokes Raman Spectroscopy (CARS) is applied to a filamentary discharge in H₂. Temperature and density profiles of molecular hydrogen are determined. The maximum temperature observed on the discharge axis is 5685 K. Vibrational and rotational transitions are analyzed and a difference in the evaluated temperatures is found which increases with pressure. In addition, the reactive thermal conductivity associated with dissociation is determined and compared with earlier work.     

Determination of temperature by stimulated raman scattering of molecular nitrogen,oxygen, and carbon dioxide

We have determined the temperature from SRS spectra of N₂-N₂, N₂-CO₂, O₂-O₂, and CO₂-CO₂ recorded in wide pressure and temperature ranges. The fitting procedure takes simultaneously into account the Dicke effect and motional narrowing. We have quantified the accuracy of the MEG and ECS-P models for rotational relaxation. The temperature extracted from each model is compared with thermocouple measurements. The influence of vibrational broadening and shifting is discussed in detail.     

Excitation of multilevel molecular systems by laser ir field

Analytical results have been obtained for some aspects of polyatomic molecular interaction with resonant ir laser radiation. The following effects are investigated by use of Schr?dinger's equation solution for natural multilevel models: the role of dynamic Stark effect in the transient region from molecular low levels to the quasi-continuum of highly excited vibrational levels; broadening of multiphoton transitions because of relatively fast decay into the quasi-continuum; threshold excitation property of multilevel systems with random detunings. Possible applications to constructing models for numerical calculations dealing with the molecule excitation problem are discussed.     

Efficient generation of tunable VUV laser radiation below 205 nm by SFM in BBO

Design and performance characteristics of a tunable dye laser system for sum frequency mixing (SFM) in a BBO crystal are presented. The system is composed of two tunable pulsed dye lasers pumped synchronously by the second harmonic of a commercial Nd:YAG laser. The radiation produced by the first dye laser is frequency doubled by second-harmonic generation (SHG) in KDP and subsequently mixed by SFM in BBO with the light of the second dye laser. The interest was focussed on generation of tunable laser radiation below 205 nm with high output power and long-time wavelength stability. High conversion efficiencies enable output energies of 100 J (20 kW) at 196 nm using only moderate Nd:YAG pump energies of 67 mJ. Altogether, a laser system with very good specifications for analytical application in the near VUV spectral region is reported.     

Influence of gas circulation on stimulated Raman scattering and amplification of ultrashort laser pulses in methane

Applying gas recirculation in a high pressure cell, laser pulses of 1 ps at 400 nm and with a repetition rate of 1 kHz were frequency shifted by stimulated Raman scattering and amplification in methane gas at high pressure. We studied the influence of gas recirculation on the conversion efficiencies into the Stokes and anti-Stokes components as well as on their spatial distributions and spectral shapes using generator and generator-amplifier arrangements. For high pump energies, recirculation in the generator cell decreases conversion efficiency into the first Stokes component whereas it increases conversion into higher Stokes and anti-Stokes components. It results in a significantly improved spatial characteristics of the frequency-shifted radiation, however, is accompanied by a substantial spectral broadening. Using gas recirculation in the generator-amplifier arrangement we achieved a conversion efficiency into the first Stokes component of about 50% with highly improved spatial and spectral characteristics.     

Rotational and vibrational temperature determination by DFWM spectroscopy

Using the DFWM technique we determined rotational and vibrational temperatures of NaH molecules in a dynamical system consisting of NaH, Na, H and H₂ for several heat-pipe oven temperatures. We applied a new way to determine the dependence of the DFWM signalI _c ^int on the power of the transition dipole momentµ without previous knowledge of the temperature. The revealed dependence isI _c ^int µ ⁴. In this case the laser intensities were found to be of the same order as the saturation intensity in accordance with simple DFWM theory. A usual Boltzmann plot was employed for the determination of the relevant rotational temperatures, which displayed higher values than the oven temperature.     

Tunable picosecond infrared pulses generated by stimulated electronic Raman scattering of a mode-locked Ti:Sapphire laser in potassium vapor

A down-conversion to the mid-infrared region by using Stimulated Electronic Raman Scattering (SERS) in potassium vapor is described. The pump radiation is a frequency-doubled regeneratively amplified Ti:Sapphire laser with a pulse duration of 2 ps, pulse energy of 0.2 mJ, and repetition rate of 10 Hz. With the pumping frequency tuned around the potassium 4s-5p transition, nearly transform-limited infrared radiation tunable between 2.2 and 3.4 m has been generated with a peak infrared energy of 12 µJ, corresponding to a quantum efficiency of 17%, and with a pulse duration of 2 ps. The present tuning range could be extended by extending the tuning range of the pump laser. In comparison, intense infrared radiation of 90 µJ energy but with a very narrow tunability around 2.9 m has also been generated by SERS in barium vapor.     

Highly efficient Raman conversion in O2 pumped by a seeded narrow band second-harmonic Nd:YAG laser

The first-Stokes conversion efficiency for a stimulated Raman scattering (SRS) is usually very low in gaseous oxygen media. In 3.0 Mpa O₂, a single longitudinal mode second harmonic Nd:YAG laser pump source gives a typical vibrational first-Stokes conversion efficiency of only 2.5%, In comparison, the accompanying stimulated Brillouin scattering (SBS) attains a reflectivity of 67%. However, by seeding an OPO beam into the Raman cavity, the first-Stokes photon conversion efficiency now attains a peak value of 54%, while the SBS reflectivity reduces to 5% in a 6.1 Mpa 41:59 O₂/ He mixture. This 54% efficiency was obtained for a seeder laser pulse-width less than one half that of pump laser (6.8 ns). A first-Stokes peak power conversion efficiency as high as 88% has been obtained when the pump and seeder pulse peaks coincide. So, we may expect a higher first-Stokes photon conversion efficiency if the seeder pulse-width can be made equal to or larger than that of the pump pulse. On the other hand, the beam quality of the first-Stokes in an O₂/ He mixture excels that of the pump laser for a seeder energy of 5 mJ and pump energy of 50 mJ. However, at pump energies higher than 105 mJ and a pump laser repetition rate of 10 Hz, the thermal defocusing effect worsens the first-Stokes beam quality. This thermal defocusing effect is a result of the Raman heat release and could be eliminated by fast circulating and cooling the Raman gas medium.     

An evaluation of precision and systematic errors in vibrational CARS thermometry

The extraction of temperatures from experimental CARS spectra is discussed and demonstrated in an electrically heated over and a low-pressure flame. The present work is focused, in particular, on how the precision of CARS thermometry is limited by the accuracy with which the experimental parameters are known, on characteristics of the diode-array detector, on saturation effects due to stimulated Raman scattering and on the influence of spectral resolution on precision and accuracy.     

Experimental study of vibrational and pure rotational coherent anti-stokes Raman scattering (CARS) in molecular hydrogen

Using a specially designed excimer-laser-pumped dye laser of adjustable bandwidth high-lying pure rotational transitions of both, ortho-and para-hydrogen have been identified by coherent anti-Stokes Raman scattering (CARS). As an interesting application H₂-based CARS-thermometry is discussed.     

Multiplex rotational CARS of N2, O2, and CO with excimer pumped dye lasers: Species identification and thermometry in the intermediate temperature range with high temporal and spatial resolution

Pure rotational CARS spectra of N₂, O₂, air, and CO have been obtained using excimer laser pumped dye-lasers. The combination of the folded BOXCARS phase matching geometry with the broad-band laser multiplex method allowed high spatial and temporal resolution. Species and concentration analysis as well as thermometry up to 700 K is demonstrated, and possible applications are discussed.     

Temperature measurements in CO2-laser-induced pyrolysis flames for SiC and ternary SiC/C/B powder synthesis by means of CARS

The hot luminescent reaction zones of CO₂-laser-induced pyrolysis flames using SiH₄/C₂H₂ gas mixtures with different silane to acetylene ratios and with and without diborane additives were investigated by means of H₂ Q-branch CARS spectroscopy, leading to spatial temperature profiles in gas flow direction. In the case of B₂H₆ additive to the stoichiometric SiH₄/C₂H₂ mixture a high temperature plateau ( 800–1000 K) of the reactant gas volume develops already several millimetres before reaching the CO₂-laser focus line. This precursor preheating zone could be explained by the catalytic effect of boron atoms or boron-containing intermediate species in the flame. A similar behaviour for acetylene-rich flames operating at half laser power was not observed.     

Collimation and decollimation of atomic beams by laser radiation

Efficient collimation and decollimation of an atomic beam by spontaneous radiation pressure acting on the atoms in axially symmtric light fields has been accomplished. The on-axic atomic-beam intensity was changed by 800 times. The entire effect of collimation and decollimation takes place in a laser-frequency variation about the natural line width.