Single‐beam coherent anti‐Stokes Raman scattering (CARS) spectroscopy of gas‐phase CO2 via phase and polarization shaping of a broadband continuum

Coherent anti‐Stokes Raman scattering (CARS) spectroscopy of gas‐phase CO₂ is demonstrated using a single femtosecond (fs) laser beam. A shaped ultrashort laser pulse with a transform‐limited temporal width of ∼7 fs and spectral bandwidth of ∼225 nm (∼3500 cm⁻¹) is employed for simultaneous excitation of the CO₂ Fermi dyads at ∼1285 and ∼1388 cm⁻¹. CARS signal intensities for the two Raman transitions and their ratio as a function of pressure are presented. The signal‐to‐noise ratio of the single beam–generated CO₂ CARS signal is sufficient to perform concentration measurements at a rate of 1 kHz. The implications of these experiments for measuring CO₂ concentrations and rapid pressure fluctuations in hypersonic and detonation‐based chemically reacting flows are also discussed. Copyright © 2010 John Wiley & Sons, Ltd.     

Flame temperature diagnostics with water lines using mid‐infrared degenerate four‐wave mixing

The feasibility of using degenerate four‐wave mixing (DFWM) for hot gas thermometry in the mid‐infrared spectral region is, for the first time, demonstrated by probing molecular ro‐vibrational transitions of water. DFWM spectra of hot water were recorded in specially designed flames, providing a series of temperatures varying from 1000 to 1900 K and, the dramatic spectral structure variations were used as temperature indicator. The intensity ratios between two hot water line groups at around 3231 cm⁻¹ were especially studied and composed into a calibration table for flame temperature measurement using DFWM spectra. The saturation properties of different lines were also studied by recording the line intensity ratios as a function of laser power, and the results indicated that saturated excitation was in favor of reliable temperature measurements. As validation, infrared DFWM spectra in an φ = 1.52 flat premixed methane/air flame were recorded, and a good temperature value was obtained. Moreover, the recently released HITEMP2010 database as well as its previous version HITEMP2000 were adopted to simulate the hot water spectra and to analyze the line intensity ratios. Copyright © 2011 John Wiley & Sons, Ltd.     

Time‐resolved investigation of the ν1 ro‐vibrational Raman band of H2CO with fs‐CARS

The technique of femtosecond time‐resolved coherent anti‐Stokes scattering (fs‐CARS) is used to investigate the strongly perturbed ν₁ ro‐vibrational Raman band of formaldehyde (H₂CO). The time‐dependent signal is simulated using a ‘Watson‐’Hamiltonian in A‐type reduction and Raman theory for asymmetric rotors. The results are compared with the experimental data. The fs‐CARS method measures the evolution of the polarization in a molecular ensemble via superposition of many states and is sensitive to spectral irregularities or line shifts of the involved transitions. ‘Coriolis’ interactions play a major role in the analysis of the ν₁ band of formaldehyde. We successfully simulate the fs‐CARS transient signal from the ν₁ band of formaldehyde including a model for multiple ‘Coriolis’ interactions, without the necessity of describing the complete interaction between all the vibrational levels. ‘Coriolis’ coupling coefficients and energy shifts are derived from the experiment by a least‐square fit. The results are discussed and compared to literature values. Copyright © 2006 John Wiley & Sons, Ltd.     

Self‐phase‐locked degenerate femtosecond optical parametric oscillator based on BiB3O6

A self‐phase‐locked degenerate femtosecond optical parametric oscillator (OPO) based on the birefringent nonlinear material, bismuth triborate, BiB₃O₆, synchronously‐pumped by a Kerr‐lens‐mode‐locked Ti:sapphire laser at 800 nm is described. By exploiting versatile phase‐matching properties of BiB₃O₆, including large spectral and angular acceptance for parametric generation and low group velocity dispersion in the optical xz plane, stable self‐phase‐locked degenerate OPO operation centered at 1600 nm is demonstrated using collinear type I (e → oo) interaction in a 1.5‐mm crystal at room temperature. The degenerate OPO output spectrum extends over 46 nm (∼5.4 THz) with 190 fs pulse duration for input pump pulses of 155 fs with a bandwidth of 7 nm. Phase coherence between the pump and degenerate output is verified using f‐2f interferometry, and discrete frequency beats caused by different carrier‐envelope‐offset frequencies are measured using radio frequency measurements. Photo shows a 1.5‐mm BiB₃O₆ crystal used as a nonlinear gain medium in a degenerate self‐phase‐locked femtosecond OPO operating at room temperature. The green beam is the result of non‐phase‐matched sum‐frequency mixing between the pump light and the sub‐harmonic OPO field at degeneracy.     

Few‐cycle,broadband, mid‐infrared optical parametric oscillator pumped by a 20‐fs Ti:sapphire laser

A few‐cycle, broadband, singly‐resonant optical parametric oscillator (OPO) for the mid‐infrared based on MgO‐doped periodically‐poled LiNbO₃ (MgO:PPLN), synchronously pumped by a 20‐fs Ti:sapphire laser is reported. By using crystal interaction lengths as short as 250 µm, and careful dispersion management of input pump pulses and the OPO resonator, near‐transform‐limited, few‐cycle idler pulses tunable across the mid‐infrared have been generated, with as few as 3.7 optical cycles at 2682 nm. The OPO can be continuously tuned over 2179‐3732 nm (4589‐2680 cm^‐1) by cavity delay tuning, providing up to 33 mW of output power at 3723 nm. The idler spectra exhibit stable broadband profiles with bandwidths spanning over 422 nm (FWHM) recorded at 3732 nm. The effect of crystal length on spectral bandwidth and pulse duration is investigated at a fixed wavelength, confirming near‐transform‐limited idler pulses for all grating interaction lengths. By locking the repetition frequency of the pump laser to a radio‐frequency reference, and without active stabilization of the OPO cavity length, an idler power stability better than 1.6% rms over >2.75 hours is obtained when operating at maximum output power, in excellent spatial beam quality with TEM₀₀ mode profile. Photograph shows a multigrating MgO:PPLN crystal used as a nonlinear gain medium in the few‐cycle femtosecond mid‐IR OPO. The visible light is the result of non‐phase‐matched sum‐frequency mixing between the interacting beams.     

Stimulated Raman spectroscopy using chirped pulses

We present a detailed theoretical and experimental characterization of a new methodology for stimulated Raman spectroscopy using two duplicates of a chirped, broadband laser pulse. Because of the linear variation of laser frequency with time (‘chirp’), when the pulses are delayed relative to one another, there exists a narrow bandwidth, instantaneous frequency difference between them, which, when resonant with a Raman‐active vibration in the sample, generates stimulated Raman gain in one pulse and inverse Raman loss in the other. This method has previously been used for coherent Raman imaging and termed ‘spectral focusing’. Here, gain and loss signals are spectrally resolved, and the spectrally integrated signals are used to determine the spectral resolution of the measured Raman spectrum. Material dispersion is used to generate a range of pulse durations, and it is shown that there is only a small change in the magnitude of the signal and the spectral resolution as the pulse is stretched from 800 to 1800 fs in duration. A quantitative theory of the technique is developed, which reproduces both the magnitude and linewidth of the experimental signals when third‐order dispersion and phase‐matching efficiency are included. The theoretical calculations show that both spectral resolution and signal magnitude are severely hampered by the third‐order dispersion in the laser pulse, and hence, a minimal amount of chirp produces the most signal with only a slight loss of spectral resolution. Copyright © 2014 John Wiley & Sons, Ltd.     

High-resolution degenerate four-wave-mixing spectroscopy of OH in a flame with a novel single-mode tunable laser

The first application of a novel single-mode tunable laser system to nonlinear spectroscopy is reported. The device uses a modeless dye laser, pumped by a single longitudinal mode (SLM) Q-switched Nd:YAG laser, as a narrow-bandwidth amplifier of the output of a SLM diode laser. The system provides pulses of 5-ns duration, 30-mJ energy and 165-MHz spectral line width tunable in the range 632–639 nm at 10-Hz repetition rate. The frequency-doubled output of the laser is used to record spectral line shapes of degenerate four wave mixing (DFWM) signals from the P₁(15) line of the A²–X² (0,0) band of OH in a methane/oxygen flame. Pressure broadening of the DFWM line shape is studied for the first time in a low-pressure flame and a pressure-broadening rate of 1.31±0.09×10^-4 cm^-1/Torr is derived from the data. Power-broadening effects are measured and compared with predictions of the standard perturbative model and of an analytical solution derived from a non-perturbative treatment of DFWM with arbitrary pump and probe intensities. PACS 42.55.Px; 42.62.Fi; 42.65.-k     

Detection of C2H2 and HCl using mid-infrared degenerate four-wave mixing with stable beam alignment: towards practical in situ sensing of trace molecular species

A stable and convenient optical system to realize the forward phase-matching geometry for degenerate four-wave mixing (DFWM) is demonstrated in the mid-infrared spectral region by measuring DFWM signals generated in acetylene (C₂H₂) and hydrogen chloride (HCl) molecules by probing the fundamental ro-vibrational transitions. IR laser pulses tunable from 2900 cm^?1 to 3350 cm^?1 with a 0.025 cm^?1 linewidth were obtained using a laser system composed of an injection seeded Nd:YAG laser, a dye laser, and a frequency mixing unit. At room temperature and atmospheric pressure, a detection limit of 35 ppm (～ 9.5×10¹⁴ molecules/cm³) for C₂H₂ was achieved in a gas flow of a C₂H₂/N₂ mixture by scanning the P(11) line of the (010(11)⁰)–(0000⁰0⁰) band. The detection limit of the HCl molecule was measured to be 25 ppm (～6.8×10¹⁴ molecules/cm³) in the same environment by probing the R(4) line. The dependences of signal intensities on molecular concentrations and laser pulse energies were demonstrated using C₂H₂ as the target species. The variations of the signal line shapes with changes in the buffer gas pressures and laser intensities were recorded and analyzed. The experimental setup demonstrated in this work facilitates the practical implementation of in situ, sensitive molecular species sensing with species-specific, spatial and temporal resolution in the spectral region of 2.7–3.3 μm (3000–3700 in cm^?1), where various molecular species important in combustion have absorption bands.     

Degenerate four-wave mixing in nitrogen dioxide: Application to combustion diagnostics

Single shot degenerate four wave mixing (DFWM) images of the distribution of nitrogen dioxide (NO₂) doped into a propane/air flame at concentrations of the order of 7000 ppm have been obtained. These images indicate the relative concentration of NO₂ in different parts of the flame with an estimated spatial resolution of 150 m.Initial experiments were performed using NO₂ in a glass cell with nitrogen buffer gas. DFWM signals were generated using both the frequency doubled output of a pulsed ND:YAG laser and the tunable blue output of an excimer pumped dye laser. The signal was investigated as a function of laser power, NO₂ concentration and buffer gas pressure. In addition, spectra of NO₂ in the region 450 to 480 nm were obtained.Signals were then sought in both a cold air/NO₂ gas flow and an ignited mixture of propane and air seeded with NO₂, using a DFWM imaging geometry. The resulting images from the flame demonstrate the disappearance of the NO₂ molecules in the flame interaction zone.This work was done when previously employed by AEA Technology at Harwell     

THz radiation generation via the interaction of two‐colour ultra‐short laser pulses with SO2 and NH3 gases

In this work, using a two‐dimensional particle‐in‐cell Monte Carlo collision computation method, terahertz (THz) radiation generation via the interaction of two‐colour, ultra‐short, high‐power laser pulses with the polyatomic molecular gases sulphur dioxide (SO₂) and ammonia (NH₃) is examined. The influence of SO₂ and NH₃ pressures and two‐colour laser pulse parameters, i.e., pulse shape, pulse duration, and beam waist, on the THz radiation generation is studied. It is shown that the THz signal generation from SO₂ and NH₃ increases with the background gas pressure. It is seen that the THz emission intensity for both gases at higher laser pulse durations is higher. Moreover, for these polyatomic gases, the plasma current density increases with increase in the laser pulse beam waist. A more powerful THz radiation intensity with a larger time to peak of the plasma current density is observed for SO₂ compared to NH₃. In addition, many THz signals with small intensities are observed for both polyatomic gases. It is seen that for both SO₂ and NH₃ the generated THz spectral intensity is higher at higher gas pressures.     

High dynamic range thermometry at 5 kHz in hydrogen–air diffusion flame using chirped‐probe‐pulse femtosecond coherent anti‐stokes Raman scattering

Chirped probe pulse femtosecond coherent anti‐Stokes Raman scattering (CPP fs‐CARS) thermometry was performed at 5 kHz in a hydrogen jet diffusion flame with an air co‐flow. Measurements were performed at different heights and radial locations within the jet diffusion flame, up to 16 nozzle exit diameters downstream (x/d = 16). The near‐nozzle measurements were characterized by large, organized, buoyancy‐driven instabilities that become more chaotic at the downstream locations x/d ≥ 4. The diffusion flame results highlight temperature fluctuations characteristic of the buoyancy‐driven Kelvin–Helmholtz‐type instability and provide new insights into the transient structure of these flames. At some measurement locations, the time‐varying temperatures ranged from 300 K to nearly 2400 K. The CPP fs‐CARS signal intensity is a factor of approximately 1000 times lower at 2400 K compared with 300 K. A dual‐channel detection system was used to increase the dynamic range of the CARS measurements. The determination of temperature from the single shot spectra is discussed in detail. Laser and detection system parameters were determined from CPP fs‐CARS spectra obtained from a near‐adiabatic laminar calibration flame apparatus. The temperature precision of the system was determined from these calibration measurements and was found to be better than 2.0% at 2200 K. The influence of an instrument response function on spectral fitting parameters is systematically assessed. Published 2015. This article is a U.S. Government work and is in the public domain in the USA.     

Sub‐picosecond Raman spectrometer for time‐resolved studies of structural dynamics in heme proteins

We describe a pump–probe Raman spectrometer based on a femtosecond Ti:sapphire laser, an optical parametric generator and two optical parametric amplifiers for time‐resolved studies, with emphasis on the structural dynamics in heme proteins. The system provides a 100‐fs pump pulse tunable in the range 500–600 nm and a transform‐limited sub‐picosecond probe pulse tunable in the range 390–450 nm. The spectrometer has spectral (25 cm⁻¹) and temporal (∼0.7 ps) resolutions which constitute an effective compromise for identifying transient heme protein species and for following their structural evolution by spontaneous Raman scattering in the time range 0.5 ps to 2 ns. This apparatus was applied to time‐resolved studies of a broad range of heme proteins, monitoring the primary dynamics of photoinduced heme coordination state and structural changes, its interaction with protein side‐chains and diatomic gaseous ligands, as well as heme vibrational cooling. The treatment of transient Raman spectra is described in detail, and the advantages and shortcomings of spontaneous resonance Raman spectroscopy for ultrafast heme proteins studies are discussed. We demonstrate the efficiency of the constructed spectrometer by measuring Raman spectra in the sub‐picosecond and picosecond time ranges for the oxygen‐storage heme protein myoglobin and for the oxygen‐sensor heme protein FixLH in interaction with the diatomic gaseous ligands CO, NO, and O₂. Copyright © 2010 John Wiley & Sons, Ltd.     

An ultrafast time‐resolved infrared and UV–vis spectroscopic and computational study of the photochemistry of acyl azides

The photochemistry of pivaloyl, benzoyl, 4‐phenylbenzoyl, and 2‐anthroyl azides has been studied using femtosecond (fs) time‐resolved infrared (TRIR) and UV–vis spectroscopy and interpreted with the aid of computational chemistry. Density functional theory calculations revealed a significant difference in the nature of the lowest singlet excited state for these carbonyl azides. The lowest singlet excited states (S₁) of p‐phenylbenzoyl and 2‐anthroyl azides are (π,π*) in nature, while the pivaloyl and benzoyl azides S₁ states involve (n,π*) excitations. Nevertheless, for all acyl azides studied here, a similar, and intense, IR band at about 2100 cm^?1 has been detected in the ultrafast TRIR experiments following 270 nm excitation. These bands were shifted to lower energy by about 100 cm^?1 relative to the N₃ stretching mode for the ground states of these azides. These 2100 cm^?1 vibrational bands were assigned to the S₁ states of acyl azides in agreement with density functional theory calculations. The decay of the acyl azide S₁ states was described by bi‐exponential functions. The fast component was attributed to the decay of the hot S₁ state and the longer component to the decay of the thermally relaxed S₁ state. A strong and broad transient absorption in the 350–650 nm spectral range was observed in the fs UV–vis experiments for p‐phenylbenzoyl and 2‐anthroyl azides. The carrier of this absorption also decayed bi‐exponentially, and the time constants were in excellent agreement with those found in the fs TRIR experiments. The slow component of the S₁ state decay was found to be dependent on the solvent polarity. When the lifetime of the acyl azide S₁ state is substantially longer than the time constant for vibrational cooling of nascent (hot) isocyanate, the correlation between the S₁ decay and isocyanate formation was clear. The 270 nm excitation populates the S_n (n ≥ 2) states of these acyl azides. It was established that a hot nitrene is produced more efficiently from both the S_n and hot S₁ states than from the relaxed S₁ state of these acyl azides. Thus, time‐resolved study provides direct experimental evidence that the S₁ state is the precursor of nitrene only when the S₁ state is pumped directly and when the S₁ state lifetime is longer than the time constant of vibrational cooling of the newborn nitrene. All of these results are consistent with the data obtained recently for 2‐napththoyl azide. Copyright © 2012 John Wiley & Sons, Ltd.     

Software for the data analysis of the arrival‐timing monitor at SACLA

X‐ray free‐electron laser (XFEL) pulses from SPring‐8 Ångstrom Compact free‐electron LAser (SACLA) with a temporal duration of <10 fs have provided a variety of benefits in scientific research. In a previous study, an arrival‐timing monitor was developed to improve the temporal resolution in pump–probe experiments at beamline 3 by rearranging data in the order of the arrival‐timing jitter between the XFEL and the synchronized optical laser pulses. This paper presents Timing Monitor Analyzer (TMA), a software package by which users can conveniently obtain arrival‐timing data in the analysis environment at SACLA. The package is composed of offline tools that pull stored data from cache storage, and online tools that pull data from a data‐handling server in semi‐real time during beam time. Users can select the most suitable tool for their purpose, and share the results through a network connection between the offline and online analysis environments.     

Ultrafast fiber lasers for strong‐field physics experiments

The recent demonstration of rare‐earth‐doped fiber lasers with a continuous‐wave output power approaching the 10‐kW level with diffraction‐limited beam quality proves that fiber lasers constitute a scalable solid‐state laser concept in terms of average power. In order to generate high peak power pulses from a fiber several fundamental limitations have to be overcome. This can be achieved by novel experimental strategies and fiber designs that offer an enormous potential towards ultrafast laser systems combining high average powers (> kW) and high peak power (> GW). In this paper the challenges, achievements and perspectives of ultrashort pulse generation and amplification in fibers are reviewed. This kind of laser system will have a tremendous impact on strong‐field physics experiments, such as the generation of coherent light by high‐harmonic generation. So far, applications in the interesting EUV spectral range suffer from the very low photon count leading to nonrelevant integration times with highly sophisticated detection schemes. High repetition rate high average power fiber lasers can potentially solve this issue. First demonstrations of high repetition‐rate strong‐field physics experiments using novel fiber laser systems will be discussed.     

Intra‐laser‐cavity microparticle sensing with a dual‐wavelength distributed‐feedback laser

An integrated intra‐laser‐cavity microparticle sensor based on a dual‐wavelength distributed‐feedback channel waveguide laser in ytterbium‐doped amorphous aluminum oxide on a silicon substrate is demonstrated. Real‐time detection and accurate size measurement of single micro‐particles with diameters ranging between 1 µm and 20 µm are achieved, which represent the typical sizes of many fungal and bacterial pathogens as well as a large variety of human cells. A limit of detection of ∼500 nm is deduced. The sensing principle relies on measuring changes in the frequency difference between the two longitudinal laser modes as the evanescent field of the dual‐wavelength laser interacts with micro‐sized particles on the surface of the waveguide. Improvement in sensitivity far down to the nanometer range can be expected upon stabilizing the pump power, minimizing back reflections, and optimizing the grating geometry to increase the evanescent fraction of the guided modes.     

Study of radiation damage induced by 12 keV X‐rays in MOS structures built on high‐resistivity n‐type silicon

Imaging experiments at the European X‐ray Free Electron Laser (XFEL) require silicon pixel sensors with extraordinary performance specifications: doses of up to 1 GGy of 12 keV photons, up to 10⁵ 12 keV photons per 200 µm × 200 µm pixel arriving within less than 100 fs, and a time interval between XFEL pulses of 220 ns. To address these challenges, in particular the question of radiation damage, the properties of the SiO₂ layer and of the Si–SiO₂ interface, using MOS (metal‐oxide‐semiconductor) capacitors manufactured on high‐resistivity n‐type silicon irradiated to X‐ray doses between 10 kGy and 1 GGy, have been studied. Measurements of capacitance/conductance–voltage (C/G–V) at different frequencies, as well as of thermal dielectric relaxation current (TDRC), have been performed. The data can be described by a dose‐dependent oxide charge density and three dominant radiation‐induced interface states with Gaussian‐like energy distributions in the silicon band gap. It is found that the densities of the fixed oxide charges and of the three interface states increase up to dose values of approximately 10 MGy and then saturate or even decrease. The shapes and the frequency dependences of the C/G–V measurements can be quantitatively described by a simple model using the parameters extracted from the TDRC measurements.     

Vibrational dynamics of nitromethane mixed with IR780 dye studied by coherent anti‐stokes Raman spectroscopy

Vibrational coupling between different kinds of molecules in liquid mixture is studied by multiplex coherent anti‐Stokes Raman spectroscopy (CARS). To identify vibrational coherence, fs‐probe with high time resolution and narrowband‐probe with high spectral resolution are adopted in CARS experiments. Using liquid nitromethane (NM) mixed with organic dye IR780 perchlorate as the sample, we can clearly observe the interference between different vibrational modes. The intermolecular vibrational interaction between NM and IR780 molecules results in the vibrational coherence transfer (VCT) in the form of a change of phase correlation. Compared with symmetric bending vibration of NO₂, coherence transfer is found to be easier to take place between C―N bond of NM and vibrations of IR780, which indicates the selectivity of intermolecular vibrational interaction. The selectivity is deduced to be related to the coordination between intramolecular and collective motion of molecules. Copyright © 2016 John Wiley & Sons, Ltd.     

SERS microRaman spectral probing of adsorbate‐containing,liquid‐overlayed nanosponge Ag aggregates assembled from fractal aggregates

Adsorbate‐containing, nanosponge Ag aggregates overlayed by a thin (~1.5 mm) liquid layer are reported as a new type of sample for Surface‐enhanced Raman scattering (SERS) microRaman spectral measurements and adsorbate (analyte) detection. Macroscopic Ag aggregates (of about 1.5 × 1.0 × 0.025 mm size) with the nanosponge internal morphology (revealed by Scanning electron microscopy (SEM)) were prepared by 3D assembling of fused fractal aggregates (D = 1.84 ± 0.04) formed in Ag nanoparticle hydrosol/HCl/adsorbate systems with 2,2’‐bipyridine (bpy) and/or a cationic free‐base tetrakis(2‐methyl‐4‐pyridiniumyl) porphine (H₂TMPyP) as the testing adsorbates. For SERS microRaman measurements, the macroscopic aggregate was overlayed by a thin (~1.5 mm) layer of the residual liquid. Preparation procedure, nanoscale imaging, and SERS spectral probing including the determination of the detection limits of the adsorbates revealed the following advantages of the adsorbate‐containing, liquid‐overlayed 3D nanosponge aggregate as a sample for SERS microRaman spectral measurements: (1) localization of adsorbate (analyte) into hot spots and, simultaneously, prevention of the analyte decomposition during the spectral measurement (carried out without an immersion objective), (2) fast and simple sample preparation, and (3) minimization of sample volume and an efficient concentration of hot spots into the focus of the laser beam. The advantages of the nanosponge Ag aggregates are further demonstrated by the 40 fmol limit of detection of bpy as Ag(0)‐bpy surface complex, as well as by preservation of the native structure of the cationic free‐base porphyrin H₂TMPyP. Copyright © 2015 John Wiley & Sons, Ltd.     

Analysis of degenerate four-wave mixing spectra of NO in a CH4/N2/O2 flame

4 /N₂/O₂ flame to spectral simulations based on a two-level theory for stationary, saturable absorbers by Abrams et al. Temperatures determined from least-squares fits of simulations to experimental spectra in the A²Σ⁺?X²Π⁺(0,0) band are compared to temperatures obtained from OH absorption spectroscopy and a radiation-corrected thermocouple. We find that DFWM rotational temperatures derived from Q-branch spectra agree with thermocouple and are independent of pump laser intensity for low to moderate saturation (I≈I_sat). However, the temperatures are systematically low and depend on pump intensity if the analysis neglects saturation effects. We demonstrate a method for obtaining an effective pump saturation intensity for use with the two-level model. This approach for analyzing saturated DFWM line intensities differs from previous work in that the use of the theory of Abrams et al. rather than a transition-dipole-moment power law allows treatment of a much wider range of saturation. Based on the observed signal-to-noise ratio an NO detection sensitivity of 25 ppm is projected, limited by a DFWM background interference specific to hydrocarbon flames. Received: 15 September 1998 / Revised version: 18 November 1998 / Published online: 24 February 1999