Coherent anti-Stokes Raman Scattering Measurements Research Articles

Enhanced double resonance Raman scattering in multilayer graphene with broadband coherent anti-Stokes Raman spectroscopy.

Graphene's unique gapless band structure and remarkably large third-order optical susceptibility have drawn significant attention to its nonlinear optical response, particularly in the context of coherent anti-Stokes Raman scattering (CARS). Under the combined influence of phononic and electronic resonances, the CARS response of graphene has been observed to exhibit a distinctive feature of time-resolved dip-to-peak evolution. Here, we report a greatly enhanced double resonance Raman mode beyond the G mode of multi-layer graphene with broadband CARS measurements. The significant difference in the intensity ratio between CARS and SR for this mode may be attributed to the preferential activation of low-frequency phonons in the impulsive stimulated Raman scattering process (ISRS) and a lower dephasing rate. Our results build on a foundation towards a deeper exploration of the coherent Raman response of two-dimensional materials.

Coherent Anti-Stokes Raman Scattering Measurements of Time and Length Scales of Temperature Fluctuations in a Turbulent Flame.

The ability to derive temporal and spatial scales of "instantaneous" local temperature variations in a turbulent flame by means of coherent anti-Stokes Raman scattering (CARS) spectroscopy is demonstrated, for the first time to our knowledge. The measurements employed two CARS spectrometers with synchronized nanosecond pulse-repetitive lasers. The system was enabling to record, with a high temporal resolution of about 10 ns, series of single laser shot CARS spectra of N2 molecules from two spatially overlapped or displaced probe volumes as small as 0.03 × 0.03 × 2 mm3. The spectra were being recorded at a variable delay between two sequential shots, following each other in pairs at a repetition rate of 10 Hz. The series of 500 coupled measurements, at the delays in the range 1 μs-10 ms and the displacements up to 2.5 mm, have been performed in a few points of an open premixed methane-air flame of a laboratory burner with the time-averaged temperatures in the range 1200-1800 K. From the spectra, "instantaneous" temperatures, at the given delay and probe volume distance, have been derived. This allowed the auto-correlation coefficients of temperature fluctuations versus the delay and the displacement to be calculated. These dependences enabled to evaluate temperature correlation times and lengths under various mixture flow rates and equivalence ratios.

Plasma-assisted deflagration to detonation transition in a microchannel with fast-frame imaging and hybrid fs/ps coherent anti-Stokes Raman scattering measurements

This study examines kinetic enhancement by nanosecond dielectric barrier discharge (ns-DBD) plasma on fuel-lean, Φ = 0.7, dimethyl ether (DME), oxygen (O2), and argon (Ar) premixture during deflagration to detonation transition (DDT) experiments in a microchannel. Nonequilibrium plasma produces active species and radicals as well as fast and slow heating of a mixture to promote ignition due to energetic electrons, ions, and electronic and vibrational excitations. Experiments are conducted to examine the influence of the plasma discharge on the premixture and on the resultant deflagration to detonation transition (DDT) onset time and distance through the use of high-speed imaging and one-dimensional, two-beam, femtosecond/picosecond, coherent anti-Stokes Raman scattering (CARS). A high-speed camera is used to trace the time histories of flame front position and velocity and to identify the dynamics and onset of DDT. The results show that plasma discharge can nonlinearly affect the onset time and distance of DDT. It is shown that a small number of plasma discharge pulses prior to ignition result in reduced DDT onset time and distance by 60% and 40%, respectively, when compared to the results without pre-excitation by ns discharges. The results also show that an increase of number of the plasma discharge pulses results in an extended DDT onset time and distance of 224% and 94%, respectively. Time history of the deflagration wave speed of DME and the analysis of ignition timescale under the choking condition of the burned gas of the deflagration wave suggest low temperature ignition may play a role for DME near the isobaric choking condition of the burned gas and the DDT. Plasma-induced low temperature oxidation of the reactive mixture is assessed via the CO2 to O2 ratio as measured through fs/ps CARS during the gas excitation in discharges. CARS measurements also confirm negligible vibrational and rotational heating of the gas by discharge. The present experiments demonstrate the ability of nonequilibrium plasma to alter the chemistry of DME/O2/Ar premixtures in order to control DDT for applications in advanced propulsion engines.

Water vapor in hydrogen flames measured by time-resolved collisional dephasing of the pure-rotational N2 CARS signal

We present a novel diagnostic technique to probe water vapor (H2O) concentration in hydrogen (H2) combustion environments via the time-resolved measurement of the collisional dephasing of the pure-rotational coherent anti-Stokes Raman scattering (CARS) signal of nitrogen (N2). The rotational Raman coherence of the N2 molecules, induced by the interaction with the pump and Stokes laser fields, dephases on a timescale of hundreds of picoseconds (ps), mostly due to inelastic collisions with other molecules in atmospheric flames. In the spatial region of H2 flames where H2O is present in appreciable amount, it introduces a faster dephasing of the N2 coherence than the other major combustion species do: we use time-resolved femtosecond/picosecond (fs/ps) CARS to deduce the H2O mole fraction from the dephasing effect of its inelastic collisions with N2. The proof-of-principle is demonstrated in a laminar H2/air diffusion flame, performing sequential measurements of the collisional dephasing of the N2 CARS signal up to 360 ps. We measure the temperature and the relative O2/N2 and H2/N2 concentrations at a short probe delay, and input the results in the time-domain model to extract the H2O mole fraction from the signal decay, thus measuring the whole scalar flow fields across the flame front. We furthermore present single-shot simultaneous thermometry and absolute concentration measurements in the turbulent TU Darmstadt/DLR Stuttgart canonical ‘H3 flame’ performed by dual-probe CARS measurements obtained with a polarization separation approach. This allows us to probe the molecular coherence simultaneously at ∼20 and ∼250 ps on the basis of a single-laser-shot, and record the resulting signals in two distinct detection channels of our unique polarization-sensitive coherent imaging spectrometer. The proposed technique allows for measuring the absolute concentrations of all the major species of H2 flames, thus providing a full characterization of the flow composition, as well as of the temperature field.

High-sensitivity frequency modulation CARS with a compact and fast tunable fiber-based light source.

Frequency modulation (FM) coherent anti-Stokes Raman scattering (CARS) is presented, using a compact as well as fast and widely tunable fiber-based light source. With this light source, Raman resonances between 700cm-1 and 3200cm-1 can be addressed via wavelength tuning within only 5 ms, which allows for FM CARS measurements with frame-to-frame wavelength switching. Moreover, the functionality for high-sensitivity FM CARS measurements was integrated by means of fiber optics to keep a stable and reliable operation. The light source accomplished FM CARS measurements with a 40 times enhanced sensitivity at a lock-in amplifier (LIA) bandwidth of 1 Hz. For fast imaging with frame-to-frame wavelength switching at a LIA bandwidth of 1 MHz, an 18-fold contrast enhancement could be verified, making this light source ideal for routine and out-of-lab FM CARS measurements for medical diagnostics or environmental sensing.

Raman Excitation of Hydrogen Molecules to v = 1 State

Coherent anti-Stokes Raman scattering (CARS) can reveal a molecule’s vibrational spectrum to a great extent. Instantaneous interaction of Stokes and pump beams stemming from powerful pulsed lasers excites a molecule’s vibrational modes in CARS. In this technique, combining two visible laser beams could create spectra resonances relating to vibrational transitions. In this work, Raman excitation of Hydrogen molecules to v = 1 state is achieved by CARS spectroscopy. CARS measurements are successfully carried out for H2 S-branch and Q-branch transitions using our laser system. This measurement proves the feasibility of CARS experiment which could be employed to excite molecules to a specific rovibrational state. Moreover, experiments conducted for CARS signal with respect to various gas pressures differing between 200 and 600 torr for S-branch transition of H2 molecule.

Vibrational CARS measurements in a near-atmospheric pressure plasma jet in nitrogen: II. Analysis

The understanding of the ro-vibrational dynamics in molecular (near)-atmospheric pressure plasmas is essential to investigate the influence of vibrational excited molecules on the discharge properties. In a companion paper Kuhfeld et al (2021 J. Phys. D: Appl. Phys. 54 305204), results of ro-vibrational coherent anti-Stokes Raman scattering (CARS) measurements for a nanosecond pulsed plasma jet consisting of two conducting molybdenum electrodes with a gap of 1 mm in nitrogen at 200 mbar are presented. Here, those results are discussed and compared to theoretical predictions based on rate coefficients for the relevant processes found in the literature. It is found, that during the discharge the measured vibrational excitation agrees well with predictions obtained from the rates for resonant electron collisions calculated by Laporta et al (2014 Plasma Sources Sci. Technol. 23 065002). The predictions are based on the electric field during the discharge, measured by electric field induced second harmonic generation Kuhfeld et al (2021 J. Phys. D: Appl. Phys. 54 305204), Lepikhin et al (2020 J. Phys. D: Appl. Phys. 54 055201) and the electron density, which is deduced from the field and mobility data calculated with Bolsig+ Hagelaar and Pitchford (2005 Plasma Sources Sci. Technol. 14 722–33). In the afterglow a simple kinetic simulation for the vibrational subsystem of nitrogen is performed and it is found, that the populations of vibrational excited states develop according to vibrational-vibrational transfer on timescales of a few microseconds, while the development on timescales of some hundred microseconds is determined by the losses at the walls. No significant influence of electronically excited states on the populations of the vibrational states visible in the CARS measurements () was observed.

Vibrational CARS measurements in a near-atmospheric pressure plasma jet in nitrogen: I. Measurement procedure and results

The non-equilibrium ro-vibrational distribution functions of molecules in a plasma can heavily influence the discharge operation and the plasma-chemistry. A convenient method for measuring the distribution function is coherent anti-Stokes Raman scattering (CARS). CARS spectra are measured in a ns-pulsed plasma between two parallel, 1 mm spaced molybdenum electrodes in nitrogen at 200 mbar with pulse durations of 200 ns/250 ns and a repetition rate of 1 kHz. The CARS spectra are analyzed by a fitting routine to extract information about the vibrational excitation of the nitrogen molecules in the plasma. It is found that during the discharge the vibrational distribution for can be described by a vibrational two-temperature distribution function. Additionally, the electric field is measured by the electric field induced second harmonic generation method during the discharge pulse. It is found to be constant in time after the initial ionization wave with values close to 81 Td for the investigated conditions. During the afterglow between two discharge pulses a more general fitting approach is used to obtain the population differences of two neighboring vibrational states. This allows to capture the more complex vibrational dynamics in that time period. The measurement results are discussed in more detail and compared to simple plasma models in a companion paper Kuhfeld et al (2021 J. Phys. D: Appl. Phys. 54 305205).

Thermalization dynamics in a pulsed microwave plasma-enhanced laminar flame

Energy transfer in a pulsed-microwave enhanced flame is investigated using hybrid fs/ps coherent anti-Stokes Raman scattering (CARS) to monitor both vibrational and rotational temperatures of nitrogen in an atmospheric pressure laminar premixed natural gas/air stagnation flame. Temperatures were measured throughout the laminar flame structure following a 30-kW peak power, 2 μs duration, 3 GHz microwave pulse in a resonant waveguide cavity. CARS measurements show a delayed increase in vibrational temperature, indicating energy loading via electron impact and subsequent energy cascade. Vibrational energy thermalization was observed over timescales faster than transport through the flame zone, but slower than predicted by known vibrational-translational rates, suggesting a long-lived pathway for increased vibrational temperature. Peak vibrational temperature increases of 100 K were observed and thermalize over 100′s of microseconds, resulting in a measurable increase in the rotational temperature over the same time interval. The magnitude of vibrational excitation and rate of thermalization in such plasma-assisted combustion environments is critical for applications including combustion ignition and control, and hybrid fs/ps CARS measurements provide the necessary detail on vibrational-translational relaxation processes of ground state nitrogen.

Spontaneous four-wave mixing in silicon nitride waveguides for broadband coherent anti-Stokes Raman scattering spectroscopy.

We present a light source for coherent anti-Stokes Raman scattering (CARS) based on broadband spontaneous four-wave mixing, with the potential to be further integrated. By using 7 mm long silicon nitride waveguides, which offer tight mode confinement and a high nonlinear refractive index coefficient, broadband signal and idler pulses were generated with 4 nJ of input pulse energy. In comparison to fiber-based experiments, the input energy and the waveguide length were reduced by two orders of magnitude, respectively. The idler and residual pump pulses were used for CARS measurements, enabling chemically selective and label-free spectroscopy over the entire fingerprint region, with an ultrafast fiber-based pump source at 1033 nm wavelength. The presented simple light source paves the path towards cost-effective, integrated lab-on-a-chip CARS applications.

Repetition frequency modulated fiber laser for coherent anti-Stokes Raman scattering

The dual-comb coherent anti-Stokes Raman scattering (CARS) technique has been proposed and developed for many years with various applications. It maps the spectral information to the time domain and resolves Raman peaks by scanning the relative delay of the pulse pair. One main drawback of this method is the low duty cycle. The span of scanning is far larger than needed, leading to a massive waste of time and energy. In this Letter, a dual-comb fiber laser system with fast repetition modulation ability is proposed and demonstrated. It can detect the relative delay via an asymmetric sum-frequency-mixing method and flip the repetition frequency difference at the exact time to increase the duty cycle by several hundred times. Consequently, it is expected that the detection efficiency is greatly enhanced compared to traditional dual-comb systems for CARS measurements.

CARS thermometry in laminar sooting ethylene-air co-flow diffusion flames with nitrogen dilution

Temperature measurements were performed in nonpremixed, sooting jet flames using coherent anti-Stokes Raman scattering (CARS). The jet fluid was ethylene diluted with different concentrations of nitrogen, and the co-flow fluid was dry air. The flames were stabilized on a Yale burner, also known as Smooke/Long burner, and the operating conditions were chosen to match previous experiments on the burner by the Yale group and other research groups. The selected flames have also been identified as target flames by the International Sooting Flame Workshop. CARS measurements of temperature provide insight into the structure of these sooting flames and serve as benchmark data for comparison with computations. A dual-pump vibrational CARS system was used here in order to avoid soot interferences. We were able to obtain high quality CARS spectra in all regions of the flame including the highly sooting regions and near the exit of the fuel nozzle, where the nonresonant modulation of the nitrogen CARS spectrum is strong due to the high ethylene concentrations. The measurements are compared with CFD results in literature and discussed in context of measured soot volume fraction, also, from literature.

Determination of N2-N2 and N2-O2 S-branch Raman linewidths using time-resolved picosecond pure rotational coherent anti-Stokes Raman scattering.

N2-N2 and N2-O2 S-branch Raman linewidths have been determined using picosecond dual-broadband pure rotational coherent anti-Stokes Raman scattering (CARS). Time-resolved rotational CARS measurements were performed in gas-phase N2 and air for temperatures up to 1900 K in order to determine the time constants of the coherence decay to subsequently calculate the S-branch Raman linewidths. Coherence decay time traces and the resulting S-branch Raman linewidths are presented for N2-N2 and N2-O2 collisions. Therewith, we reduce the gap of widely missing S-branch linewidth data in the temperature regime of many combustion processes. Further, we demonstrate that the standard monoexponential fitting of the coherence decay, as it is commonly done for nitrogen, is not applicable to oxygen.

Dual-pump CARS measurements in a hydrogen diffusion flame in cross-flow with AC dielectric barrier discharge

This paper presents dual-pump coherent anti-Stokes Raman scattering (CARS) measurements for simultaneous detection of flow temperature and relative concentration, applied to the characterization of a discharge-coupled reacting jet in a cross flow. The diagnostic is hydrogen Q-branch based, providing a much wider dynamic range compared to detection in the S-branch. For a previously developed dielectric barrier discharge, aligned co-axially with the fuel jet, OH planar laser induced fluorescence measurements show that the disturbance in the flame boundary leads to mixing enhancement. The H2-N2 dual-pump CARS measurement was used to map two-dimensional temperature distributions. The increase of the maximum temperature was up to 300 K, with 50% more H2 consumption, providing the reason for the decrease in the flame length by 25%. The increase of the relative H2O-H2 fraction was accompanied with a temperature increase, which indicates local equivalence ratios of below 1. The H2-O2 dual-pump measurements confirmed that the fuel-oxidizer ratios remain in the fuel-lean side at most of the probed locations.

Stain-free Histopathology of Basal Cell Carcinoma by Dual Vibration Resonance Frequency CARS Microscopy.

Basal cell carcinoma (BCC) is the most common malignancy in Caucasians. Nonlinear microscopy has been previously utilized for the imaging of BCC, but the captured images do not correlate with H&E staining. Recently, Freudiger et al. introduced a novel method to visualize tissue morphology analogous to H&E staining, using coherent anti-Stokes Raman scattering (CARS) technique. In our present work, we introduce a novel algorithm to post-process images obtained from dual vibration resonance frequency (DVRF) CARS measurements to acquire high-quality pseudo H&E images of BCC samples. We adapted our CARS setup to utilize the distinct vibrational properties of CH3 (mainly in proteins) and CH2 bonds (primarily in lipids). In a narrowband setup, the central wavelength of the pump laser is set to 791nm and 796nm to obtain optimal excitation. Due to the partial overlap of the excitation spectra and the 5-10nm FWHM spectral bandwidth of our lasers, we set the wavelengths to 790nm (proteins) and 800nm (lipids). Nonresonant background from water molecules also reduces the chemical selectivity which can be significantly improved if we subtract the DVRF images from each other. As a result, we acquired two images: one for "lipids" and one for" proteins" when we properly set a multiplication factor to minimize the non-specific background. By merging these images, we obtained high contrast H&E "stained" images of BBC's. Nonlinear microscope systems upgraded for real time DVRF CARS measurements, providing pseudo H&E images can be suitable for in vivo assessment of BCC in the future.

Three-color vibrational CARS thermometry of fuel-rich ethylene/air flames using a potassium gadolinium tungstate Raman-active crystal as a source of narrowband probe radiation.

Three-color broadband vibrational coherent anti-Stokes Raman scattering (CARS) temperature measurements were carried out in laminar fuel-rich sooting ethylene/air flames. Stimulated Raman scattering (SRS) of a picosecond pump laser pulse in a Raman-active potassium gadolinium tungstate [KGd(WO4)2] crystal was employed as a source of narrowband probe radiation. In the three-color CARS experiment, this wavelength-shifted radiation enables N2-based vibrational CARS temperature measurements in sooting flames free of the signal interference with the absorption/emission bands of the flame intermediate radicals C2. Spatial temperature profiles for different fuel-rich atmospheric pressure ethylene/air flames are presented in comparison with the results of two-color broadband vibrational and dual-broadband pure rotational CARS temperature measurements. The comparison shows the suitability of the three-color CARS measurement technique employing the KGd(WO4)2 crystal for accurate, C2 interference-free, temperature measurements in sooting flames.

Viewing Cancer in a New Light: Multimodal Label-Free Specific Chemical Imaging to Distinguish Healthy Cell Tissue from Invasive Carcinoma

Microscopy has always been an important tool when determining whether a biopsy contains invasive carcinomas. For this purpose, light microscopy is often used due to its simplicity in construction and operation. The downside to this is the time lost in preparing biopsies before imaging. Typically, the process of obtaining a biopsy, molding, sectioning, mounting and staining of the biopsy on microscopy glass slides and finally imaging the biopsy takes between 6-10 days. If the preparatory steps could be eliminated, valuable time would be freed. Coherent anti-Stokes Raman Scattering (CARS) microscopy offers a possible solution to this obstacle. CARS is a non-linear optical microscopy technique that allows label-free specific imaging of chemical moieties present in a sample. Specifically, lipids (rich in CH2-moieties) and protein (rich in CH-moieties), as well as water, are easily imaged using CARS. A system capable of performing CARS microscopy will generally also be capable of doing Second-Harmonic Imaging Microscopy (SHIM). This technique uses second-harmonic generation (SHG) to achieve frequency doubling of the incident light. SHIM enables imaging of biological structures, which possess the characteristics of being both highly polarizable and ordered on medium to long length scales. Specifically collagen, which is present especially in the basement membrane, is very capable of producing a second-harmonic signal. By combining CARS, SHIM and multi-photon excitation of auto-fluorescent molecules, it is possible to acquire multimodal micrographs of epithelial tissue samples. The CARS measurements gives a unique insight into cell organization in tissue by clearly visualizing the cell membrane bilayer and lipid distribution, while the SHIM reveals the location of the basement membrane and underlying connecting tissue. Our results show that it is possible, in an unlabeled sample, to differentiate between healthy tissue samples and samples that display varying degrees of dysplasia or invasive carcinomas. This opens up for the possibility for future fast bedside cancer diagnostics using CARS microscopy.

Temperature measurements in metalized propellant combustion using hybrid fs/ps coherent anti-Stokes Raman scattering.

We apply ultrafast pure-rotational coherent anti-Stokes Raman scattering (CARS) for temperature and relative oxygen concentration measurements in the plume emanating from a burning, aluminized ammonium-perchlorate propellant strand. Combustion of these metal-based propellants is a particularly hostile environment for laser-based diagnostics, with intense background luminosity and scattering from hot metal particles as large as several hundred micrometers in diameter. CARS spectra that were previously obtained using nanosecond pulsed lasers in an aluminum-particle-seeded flame are examined and are determined to be severely impacted by nonresonant background, presumably as a result of the plasma formed by particulate-enhanced laser-induced breakdown. Introduction of femtosecond/picosecond (fs/ps) laser pulses improves CARS detection by providing time-gated elimination of strong nonresonant background interference. Single-laser-shot fs/ps CARS spectra were acquired from the burning propellant plume, with picosecond probe-pulse delays of 0 and 16 ps from the femtosecond pump and Stokes pulses. At zero delay, nonresonant background overwhelms the Raman-resonant spectroscopic features. Time-delayed probing results in the acquisition of background-free spectra that were successfully fit for temperature and relative oxygen content. Temperature probability densities and temperature/oxygen correlations were constructed from ensembles of several thousand single-laser-shot measurements with the CARS measurement volume positioned within 3 mm or less of the burning propellant surface. The results show that ultrafast CARS is a potentially enabling technology for probing harsh, particle-laden flame environments.

Spontaneous and coherent anti-Stokes Raman spectroscopy of human gastrocnemius muscle biopsies in CH-stretching region for discrimination of peripheral artery disease.

Peripheral Artery Disease (PAD) is a common manifestation of atherosclerosis, characterized by lower leg ischemia and myopathy in association with leg dysfunction. In the present study, Spontaneous and coherent anti-Stokes Raman scattering (CARS) spectroscopic techniques in CH-stretching spectral region were evaluated for discriminating healthy and diseased tissues of human gastrocnemius biopsies of control and PAD patients. Since Raman signatures of the tissues in the fingerprint region are highly complex and CH containing moieties are dense, CH-stretching limited spectral range was used to classify the diseased tissues. A total of 181 Raman spectra from 9 patients and 122 CARS spectra from 12 patients were acquired. Due to the high dimensionality of the data in Raman and CARS measurements, principal component analysis (PCA) was first performed to reduce the dimensionality of the data (6 and 9 principal scores for Raman and CARS, respectively) in the CH-stretching region, followed by a discriminant function analysis (DFA) to classify the samples into different categories based on disease severity. The CH2 and CH3 vibrational signatures were observed in the Raman and CARS spectroscopy. Raman and CARS data in conjunction with PCA-DFA analysis were capable of differentiating healthy and PAD gastrocnemius with an accuracy of 85.6% and 78.7%, respectively.

Hybrid fs/ps rotational CARS temperature and oxygen measurements in the product gases of canonical flat flames

A hybrid fs/ps pure-rotational coherent anti-Stokes Raman scattering (CARS) scheme is systematically evaluated over a wide range of flame conditions in the product gases of two canonical flat-flame burners. Near-transform-limited, broadband femtosecond pump and Stokes pulses impulsively prepare a rotational Raman coherence, which is later probed using a high-energy, frequency-narrow picosecond beam generated by the second-harmonic bandwidth compression scheme that has recently been demonstrated for rotational CARS generation in H2/air flat flames. The measured spectra are free of collision effects and nonresonant background and can be obtained on a single-shot basis at 1kHz. The technique is evaluated for temperature/oxygen measurements in near-adiabatic H2/air flames stabilized on the Hencken burner for equivalence ratios of φ=0.20–1.20. Thermometry is demonstrated in hydrocarbon/air products for φ=0.75–3.14 in premixed C2H4/air flat flames on the McKenna burner. Reliable spectral fitting is demonstrated for both shot-averaged and single-laser-shot data using a simple phenomenological model. Measurement accuracy is benchmarked by comparison to adiabatic-equilibrium calculations for the H2/air flames, and by comparison with nanosecond CARS measurements for the C2H4/air flames. Quantitative accuracy comparable to nanosecond rotational CARS measurements is observed, while the observed precision in both the temperature and oxygen data is extraordinarily high, exceeding nanosecond CARS, and on par with the best published thermometric precision by femtosecond vibrational CARS in flames, and rotational femtosecond CARS at low temperature. Threshold levels of signal-to-noise ratio to achieve 1–2% precision in temperature and O2/N2 ratio are identified. The results show that pure-rotational fs/ps CARS is a robust and quantitative tool when applied across a wide range of flame conditions spanning lean H2/air combustion to fuel-rich sooting hydrocarbon flames.