Pure-rotational Coherent anti-Stokes Raman Spectroscopy Research Articles

Simultaneous Temperature and Pressure Measurements in Compressible Flow Using Nanosecond O2 Coherent Anti-Stokes Raman Spectroscopy.

Simultaneous pure-rotational coherent anti-Stokes Raman spectroscopy (PRCARS) and vibrational O2 CARS spectroscopy (VCARS) were performed at elevated pressure and lowered temperature conditions in non-reacting compressible flow. We applied dual-pump CARS in a three-laser, three-color configuration to simultaneously acquire the PRCARS and VCARS spectra of O2. PRCARS spectra provide excellent sensitivity to temperature at relatively low temperatures. Pressure was extracted using the differential response of collisional effects in the PRCARS and the VCARS spectra. We used an under-expanded jet outside a choked converging nozzle as the compressible flow-field. We numerically analyze the pressure sensitivity of the combined CARS technique. Finally, we compare the collisional narrowing lineshape models of rotational diffusion narrowing and modified-exponential-gap model, for fitting the experimental spectrum.

Pure-rotational 1D-CARS spatiotemporal thermometry with a single regenerative amplifier system.

We report spatiotemporal pure-rotational coherent anti-Stokes Raman spectroscopy (CARS) in a one-dimensional imaging arrangement obtained with a single ultrafast regenerative amplifier system. The femtosecond pump/Stokes photon pairs, used for impulsive excitation, are delivered by an external compressor operating on a ∼35% beam split of the uncompressed amplifier output (2.5 mJ/pulse). The picosecond 1.2 mJ probe pulse is produced via the second-harmonic bandwidth compression (SHBC) of the ∼65% remainder of the amplifier output (4.5 mJ/pulse), which originates from the internal compressor. The two pump/Stokes and probe pulses are spatially, temporally, and repetition-wise correlated at the measurement, and the signal generation plane is relayed by a wide-field coherent imaging spectrometer onto the detector plane, which is refreshed at the same repetition rate as the ultrafast regenerative amplifier system. We demonstrate 1 kHz cinematographic 1D-CARS gas-phase thermometry across an unstable premixed methane/air flame-front, achieved with a single-shot precision <1% and accuracy <3%, 1.4 mm field of view, and an excellent <20µm line-spread function.

Hybrid femtosecond/picosecond pure rotational anti-Stokes Raman spectroscopy of nitrogen at high pressures (1–70 atm) and temperatures (300–1000 K)

We demonstrate hybrid femtosecond/picosecond (fs/ps) pure-rotational coherent anti-Stokes Raman spectroscopy (RCARS) at high temperatures and pressures. Pulse-shaper-produced 40 fs pulses and bandwidth-narrowed, frequency-upconverted 5 ps pulses interact in a high-pressure cell containing N2 at 1–70 atm and 300–1000 K. Accurate experimental temperatures evaluated from fits to model rotational spectra confirm that the sensitivity and precision advantages of hybrid fs/ps RCARS can be exploited in characterizing combustion environments, even in the pressure regime where significant collisional energy transfer and line broadening cannot be neglected.

Pure-rotational H2 thermometry by ultrabroadband coherent anti-Stokes Raman spectroscopy.

Coherent anti-Stokes Raman spectroscopy (CARS) is a sensitive technique for probing highly luminous flames in combustion applications to determine temperatures and species concentrations. CARS thermometry has been demonstrated for the vibrational Q-branch and pure-rotational S-branch of several small molecules. Practical advantages of pure-rotational CARS, such as multi-species detection, reduction of coherent line mixing and collisional narrowing even at high pressures, and the potential for more precise thermometry, have motivated experimental and theoretical advances in S-branch CARS of nitrogen (N2), for example, which is a dominant species in air-fed combustion processes. Although hydrogen (H2) is of interest given its prevalence as a reactant and product in many gas-phase reactions, laser bandwidth limitations have precluded the extension of CARS thermometry to the H2 S-branch. We demonstrate H2 thermometry using hybrid femtosecond/picosecond pure-rotational CARS, in which a broadband pump/Stokes pulse enables simultaneous excitation of the set of H2 S-branch transitions populated at flame temperatures over the spectral region of 0-2200 cm-1. We present a pure-rotational H2 CARS spectral model for data fitting and compare extracted temperatures to those from simultaneously collected N2 spectra in two systems of study: a heated flow and a diffusion flame on a Wolfhard-Parker slot burner. From 300 to 650 K in the heated flow, the H2 and N2 CARS extracted temperatures are, on average, within 2% of the set temperature. For flame measurements, the fitted H2 and N2 temperatures are, on average, within 5% of each other from 300 to 1600 K. Our results confirm the viability of pure-rotational H2 CARS thermometry for probing combustion reactions.

Raman linewidth measurements using time-resolved hybrid picosecond/nanosecond rotational CARS.

We report an innovative approach for time-domain measurements of S-branch Raman linewidths using hybrid picosecond/nanosecond pure-rotational coherent anti-Stokes Raman spectroscopy (RCARS). The Raman coherences are created by two picosecond excitation pulses and are probed using a narrow-band nanosecond pulse at 532 nm. The generated RCARS signal contains the entire coherence decay in a single pulse. By extracting the decay times of the individual transitions, the J-dependent Raman linewidths can be calculated. Self-broadened S-branch linewidths for nitrogen and oxygen at 293 K and ambient pressure are in good agreement with previous time-domain measurements. Experimental considerations of the approach are discussed along with its merits and limitations. The approach can be extended to a wide range of pressures and temperatures and has potential for simultaneous single-shot thermometry and linewidth determination.

Two-stage energy thermalization mechanism in nanosecond pulse discharges in air and hydrogen–air mixtures

Time-resolved and spatially resolved temperature measurements, by pure rotational picosecond broadband coherent anti-Stokes Raman spectroscopy (CARS), and kinetic modeling calculations are used to study kinetics of energy thermalization in nanosecond pulse discharges in air and hydrogen–air mixtures. The diffuse filament, nanosecond pulse discharge (pulse duration ∼100 ns) is sustained between two spherical electrodes and is operated at a low pulse repetition rate to enable temperature measurements over a wide range of time scales after the discharge pulse. The experimental results demonstrate high accuracy of pure rotational ps CARS for thermometry measurements in highly transient non-equilibrium plasmas. Rotational–translational temperatures are measured for time delays after the pulse ranging from tens of ns to tens of ms, spanning several orders of magnitude of time scales for energy thermalization in non-equilibrium plasmas. In addition, radial temperature distributions across the plasma filament are measured for several time delays after the discharge pulse. Kinetic modeling calculations using a state-specific master equation kinetic model of reacting hydrogen–air plasmas show good agreement with experimental data. The results demonstrate that energy thermalization and temperature rise in these plasmas occur in two clearly defined stages, (i) ‘rapid’ heating, caused by collisional quenching of excited electronic states of N2 molecules by O2, and (ii) ‘slow’ heating, caused primarily by N2 vibrational relaxation by O atoms (in air) and by chemical energy release during partial oxidation of hydrogen (in H2–air). The results have major implications for plasma assisted combustion and plasma flow control.

Pure rotational Coherent anti‐Stokes Raman spectroscopy of water vapor and its relevance for combustion diagnostics

In this work, we report for the first time the rotational coherent anti‐Stokes Raman spectroscopy (CARS) spectrum of water vapor, recorded through experiments at 400 K and 670 K for Raman shifts up to 600 cm−1. Using the standard dual‐broadband pure rotational CARS approach, the resonant structure was overwhelmed by a strong non‐resonant background. By employing a polarization technique, this background could be suppressed and the resonant structure discerned. The spectral line structure matched spectra from spontaneous rotational Raman scattering found in the literature. The CARS signal intensity at the highest peak from water vapor at 400 K was more than five orders of magnitude weaker than for N2 because of a low Raman cross section and a larger number of transitions. Due to the weak resonant signal, water vapor is an unsuitable candidate for CARS thermometry and relative concentration measurements in combustion. Still, rotational CARS spectra from product gases in combustion will be affected by the presence of water, which is briefly discussed. Copyright © 2013 John Wiley &amp; Sons, Ltd.

High-spatial-resolution one-dimensional rotational coherent anti-Stokes Raman spectroscopy imaging using counterpropagating beams

A counterpropagating phase-matching geometry is employed for high-spatial-resolution one-dimensional (1D) imaging of temperature and O2-to-N2 concentration ratio using picosecond pure-rotational coherent anti-Stokes Raman spectroscopy (RCARS) over a large field (20 mm). A single-shot 1D RCARS image of more than 20 mm in length is thus acquired at 300 K in air. High-resolution 1D RCARS flame measurements are demonstrated using a custom-built burner and a premixed methane/air flame (Φ=0.6). This phase-matching scheme improves the spatial resolution by approximately 1 order of magnitude when compared to the standard small-angle BOXCARS phase-matching schemes typically employed in CARS measurements. Additionally, for a 20 mm 1D image, signal levels are increased by 10(2) because of the higher irradiance provided in the current scheme.

Quantitative one-dimensional imaging using picosecond dual-broadband pure-rotational coherent anti-Stokes Raman spectroscopy

We employ picosecond dual-broadband pure-rotational coherent anti-Stokes Raman spectroscopy (CARS) in a one-dimensional (1D) imaging configuration. Temperature and O(2):N(2) concentration ratios are measured along a 1D line of up to 12 mm in length. The images consist of up to 330 individual rotational CARS (RCARS) spectra, corresponding to 330 spatially resolved volume elements in the probe volume. Signal levels are sufficient for the collection of single-laser-pulse images at temperatures of up to approximately 1200 K and shot-averaged images at flame temperatures, demonstrated at 2100 K. The precision of picosecond pure-rotational 1D imaging CARS is assessed by acquiring a series of 100 single-laser-pulse images in a heated flow of N(2) from 410 K-1200 K and evaluating a single volume element for temperature in each image. Accuracy is demonstrated by comparing temperatures from the evaluated averaged spectra to thermocouple readings in the heated flow. Deviations from the thermocouple of <30 K in the evaluated temperature were found at up to 1205 K. Accuracy and single-shot precision are compared to those reported for single-point nanosecond dual-broadband pure-RCARS and nanosecond 1D vibrational CARS.

Picosecond time-resolved pure-rotational coherent anti-Stokes Raman spectroscopy in sooting flames

The development of time-resolved dual-broadband pure-rotational coherent anti-Stokes Raman spectroscopy using picosecond laser pulses is investigated for use in the study of highly sooting flames. Axi-symmetric ethylene and propane diffusion flames were studied. Suppression of nonresonant and Raman resonant interference signals is demonstrated by delaying the probe pulse beyond the temporal envelope of the pump pulses, and these spectra are compared with those obtained using conventional polarization-based interference suppression techniques. Flame profiles for both temperature and the O2 to N2 ratio are obtained. Evaluated temperatures are corrected for delay-induced spectral heating and compared to published thermocouple measurements.

Suppression of Raman-resonant interferences in rotational coherent anti-Stokes Raman spectroscopy using time-delayed picosecond probe pulses

We measure time-dependent pure-rotational coherent anti-Stokes Raman spectroscopy (CARS) spectra for room-temperature N(2), O(2), CO(2), C(2)H(4), and C(3)H(8), as well as in a C(3)H(8) diffusion flame, using picosecond lasers. Because Raman coherences for N(2) and O(2) persist significantly longer than those for the other species, delayed probing can significantly reduce unwanted resonant contributions to rotational coherent anti-Stokes Raman spectroscopy spectra, enabling temperature and relative O(2)/N(2) concentration determination in fuel-rich gas mixtures. Delayed probing also eliminates interference from smeared vibrational CARS. Probe delay affects both the temperature and relative O(2)/N(2) concentrations inferred from rotational spectra when using a standard frequency-domain analysis.

Picosecond time-resolved pure-rotational coherent anti-Stokes Raman spectroscopy for N_2 thermometry

Time-resolved pure-rotational coherent anti-Stokes Raman spectroscopy using picosecond-duration laser pulses is investigated for gas thermometry. The use of picosecond laser pulses significantly reduces background caused by scattering of the probe beam, and delayed probing of the Raman coherence enables elimination of interference from nonresonant four-wave mixing processes. Temperatures inferred from rotational spectra are sensitive to the probe delay because of the rotational-level dependence of collisional dephasing of Raman coherences. The sensitivity decreases, however, with increasing temperature, and accurate temperature measurements in a flame are demonstrated using a standard frequency-domain analysis of the spectra.

Thermometry for turbulent flames by coherent anti-Stokes Raman spectroscopy with simultaneous referencing to the modeless excitation profile

An optimal system for temperature measurements by coherent anti-Stokes Raman spectroscopy (CARS) in turbulent flames and flows is presented. In addition to a single-mode pump laser and a modeless dye laser, an echelle spectrometer with a cross disperser is used. This system permits simultaneous measurement of the N2 CARS spectrum and the broadband dye laser profile. A procedure is developed to use software to transform this profile into the excitation profile by which the spectrum is referenced. Simultaneous shot-to-shot referencing is compared to sequential averaged referencing for data obtained in flat flames and in room air. At flame temperatures, the resultant 1.5% imprecision is limited by flame fluctuations, indicating that the system may have a single-shot imprecision below 1%. At room temperature, the 3.8% single-shot imprecision is of the same order as the best values reported for dual-broadband pure-rotational CARS. Using the unique shot-to-shot excitation profiles, simultaneous referencing eliminates systematic errors. At 2000 and 300 K, the 95% confidence intervals are estimated to be +/- 20 and +/- 10 K, respectively.

Application of an optical pulse stretcher to coherent anti-Stokes Raman spectroscopy

An external optical cavity pulse stretcher for nanosecond-long laser pulses has been applied to coherent anti-Stokes Raman spectroscopy (CARS). An increased signal-to-noise ratio was achieved for both vibrational and pure rotational CARS, while the power density of the laser beams remained constant. Moreover, it was demonstrated that the use of the pulse stretcher also leads to improved precision of the determined temperatures and concentrations as a result of repeated excitation of the dye laser.

High‐pressure pure rotational CARS: comparison of temperature measurements with O2, N2 and synthetic air

AbstractThe accuracy of pure rotational coherent anti‐Stokes Raman spectroscopy (CARS) temperature measurements was investigated using O2, N2 and synthetic air for comparison. These measurements were performed in a high‐pressure cell for pressures between 0.1 and 15 MPa. The cell temperature was varied between 300 to 700 K. The temperature values deduced from the pure rotational CARS S‐branch of O2 are in good agreement with the reference thermocouple reading. For the temperature and pressure range investigated, the accuracy for O2 measurements was better than that obtained for N2 and synthetic air. Copyright © 2003 John Wiley &amp; Sons, Ltd.

Simultaneous vibrational and pure rotational coherent anti-stokes Raman spectroscopy for temperature and multispecies concentration measurements demonstrated in sooting flames.

The potential of measuring temperature and multiple species concentrations (N2, O2, CO) by use of combined vibrational coherent anti-Stokes Raman spectroscopy (CARS) and pure rotational CARS has been investigated. This was achieved with only one Nd:YAG laser and one dye laser together with a single spectrograph and CCD camera. From measurements in premixed sooting C2H4-air flames it was possible to evaluate temperatures from both vibrational CARS and rotational CARS spectra, O2 concentration from the rotational CARS spectra, and CO concentration from the vibrational CARS spectra. Quantitative results from premixed sooting C2H4-air flames are presented, and the uncertainties in the results as well as the possibility of extending the combined CARS technique for probing of additional species are discussed.

Temperature measurements in convective heat transfer flows using dual-broadband, pure-rotational coherent anti-Stokes Raman spectroscopy (CARS)

This paper describes the use of dual-broadband, pure-rotational coherent anti-Strokes Raman spectroscopy (CARS) as a non-intrusive temperature diagnostic for convective-heat-transfer flows. The characteristics of the dual-broadband, pure-rotational CARS technique are discussed, and the technique is compared to other temperature measurement methods. Dual-broadband, pure-rotational CARS was used to measure mean temperature profiles in a low-Reynolds-number, turbulent boundary layer. The results are presented in wall units and compared to the thermal law of the wall for zero-pressure-gradient boundary layers. Temperature data were acquired as close as 50 μm (±25 μm) to the wall, with a spatial resolution of 50 μm normal to the heat transfer surface, and a 2σ precision limit of ±4 K. The spatial resolution of this experimental method provides detailed information in complex thermal boundary layers and allows for an estimation of the convective heat flux to within an estimated uncertainty of −5% to +25%. Single-laser-shot temperature data were acquired in a gas cell, and the potential for measurement of rms temperature fluctuations is discussed in terms of the resulting probability density functions.

Oxygen concentration and temperature measurements in N2?O2 mixtures using rotational coherent anti-Stokes Raman spectroscopy

The accuracy and precision of oxygen concentration and temperature measured by dual-broadband rotational Coherent Anti-Stokes Raman Spectroscopy (CARS) were investigated in nitrogen-oxygen mixtures at atmospheric pressure and temperatures between 290 and 1410 K. The relative standard deviation of temperatures evaluated from pure oxygen rotational CARS spectra was found to be around 5%, and the mean temperature was the same as for nitrogen CARS spectra, except for temperatures above 1000 K, where the temperature was 120 K below the correct value. The in situ calibrated oxygen concentrations were within 10% of the correct value, with a standard deviation of around 1.2% for the mixtures of 12 and 20% oxygen in nitrogen. For the lowest oxygen concentrations considered in this study (2 and 4%), the systematic errors in the evaluated concentrations were very large, and the standard deviation of repeated single-shot measurements was above 2%. However, employing weighting in the spectral fitting routine reduced the errors in the concentration and the single-shot standard deviation was lowered to 0.5%. Finally, it was shown that spectral interference (from oxygen) in a rotational CARS spectrum of nitrogen generally had little impact on the temperature evaluated from fitting the spectra to theoretical nitrogen spectra.

Simultaneous rotational coherent anti-Stokes Raman spectroscopy and coherent Stokes Raman spectroscopy with arbitrary pump–Stokes spectral separation

A new approach to pure rotational coherent anti-Stokes Raman spectroscopy (CARS) and coherent Stokes Raman spectroscopy (CSRS) is demonstrated in which the pump and broadband Stokes lasers that are mixed have a large and arbitrary spectral separation. In this method, the rotational Raman coherences are established by different frequency components within the single, broadband Stokes source. The narrow band then scatters from the excited coherences, producing CARS and CSRS simultaneously. We discuss phase matching for this new technique and its inherent advantages relative to pure rotational CARS as normally implemented.