Broadband, background-free methane absorption in the mid-infrared.

Rotationally resolved, broadband absorption spectra of the fundamental vibrational transition of the asymmetric C-H stretch mode of methane are measured under single-laser-shot conditions using time-resolved optically gated absorption (TOGA). The TOGA approach exploits the difference in timescales between a broadband, fs-duration excitation source and the ps-duration absorption features induced by molecular absorption to allow effective suppression of the broadband background spectrum, thereby allowing for sensitive detection of multi-transition molecular spectra. This work extends the TOGA approach into the mid-infrared (mid-IR) spectral regime, allowing access to fundamental vibrational transitions while providing broadband access to multiple mid-IR transitions spanning ∼150 cm-1 (∼160 nm) near 3.3 µm, thereby highlighting the robustness of this technique beyond previously demonstrated electronic spectroscopy. Measurements are conducted in a heated gas cell to determine the accuracy of the simultaneous temperature and species-concentration measurements afforded by this single-shot approach in a well-characterized environment. Application of this approach toward fuel-rich methane-nitrogen-oxygen flames is also demonstrated.

Resonance-enhanced, rare-gas-assisted femtosecond-laser electronic-excitation tagging in argon/nitrogen mixtures.

Multiphoton-resonance enhancement of a rare-gas-assisted nitrogen femtosecond-laser electronic-excitation-tagging (FLEET) signal is demonstrated. The FLEET signal is ideal for velocimetric tracking of nitrogen gas in flow environments by virtue of its long-lived nature. By tuning to three-photon-resonant transitions of argon, energy can be more efficiently deposited into the mixture, thereby producing a stronger and longer-lived FLEET signal following subsequent efficient energy transfer from excited-state argon to the C (3Πu) excited state of nitrogen. Such resonant excitation exhibits as much as an order of magnitude increase in this rare-gas-assisted FLEET signal, compared to near-resonance excitation of seeded argon demonstrated in previous work, while reducing the required input excitation-pulse energies by two orders of magnitude compared to traditional FLEET.

Concentration and pressure scaling of CH2O electronic-resonance-enhanced coherent anti-Stokes Raman scattering signals.

Nanosecond electronic-resonance-enhanced coherent anti-Stokes Raman scattering (ERE-CARS) is evaluated for the measurement of formaldehyde (CH2O) concentrations in reacting and nonreacting conditions. The three-color scheme utilizes a 532 nm pump beam and a scanned Stokes beam near 624 nm for Raman excitation of the C-H symmetric stretch (ν1) vibrational mode; further, a 342 nm resonant probe is tuned to produce the outgoing CARS signal via the 101403 vibronic transition between the ground (X~1A1) and first excited (A~1A2) electronic states. This allows detection of CH2O at concentrations as low as 9×1014molecules/cm3 (55 parts per million) in a calibration cell with CH2O and N2 at 1 bar and 450 K with 3% uncertainty. The measurements show a quadratic dependence of the signal with CH2O number density. Pressure scaling experiments up to 11 bar in the calibration cell show an increase in signal up to 8 bar. We study pressure dependence up to 11 bar and further apply the technique to characterize the CH2O concentration in an atmospheric premixed dimethyl ether/air McKenna burner flame, with a maximum concentration uncertainty of 11%. This approach demonstrates the feasibility for spatially resolved measurements of minor species such as CH2O in reactive environments and shows promise for application in high-pressure combustors.

100 kHz krypton-based flow tagging velocimetry in a high-speed flow.

Krypton (Kr)-based tagging velocimetry is demonstrated in a Kr/N2 jet at 100 kHz repetition rate using a custom-built burst-mode laser and optical parametric oscillator (OPO) system. At this repetition rate, the wavelength-tunable, narrow linewidth laser platform can generate up to 7 mJ/pulse at resonant Kr two-photon-excitation wavelengths. Following a comprehensive study, we have identified the 212.56 nm two-photon-excitation transition as ideal for efficient Kr-based velocimetry, producing a long-lived (∼40µs) fluorescence signal from single-laser-pulse tagging that is readily amenable to velocity tracking without the need for a second "read" laser pulse. This long-lived fluorescence signal is found to emanate from N2-rather than from Kr-following efficient energy transfer. Successful flow velocity tracking is demonstrated at multiple locations in a high-speed Kr/N2 jet flow. The 100 kHz repetition rate provides the ability to perform time-resolved velocimetry measurements in high-speed and even hypersonic flow environments, where standard velocimetry approaches are insufficient to capture the relevant dynamics.

Comparison of femtosecond and nanosecond two-photon-absorption laser-induced fluorescence of krypton.

Two-photon-absorption laser-induced fluorescence of Kr was explored using both nanosecond- and femtosecond-duration laser excitation sources. Fluorescence signals following two-photon excitation at two wavelengths (212.56 nm and 214.77 nm) were compared while varying laser pulse duration, energy, and excitation wavelength as well as pressure and Kr mole fraction in mixtures with nitrogen. Our findings show that stronger fluorescence was observed when the excitation wavelength was tuned to 212.56 nm, regardless of the excitation-pulse duration. Moreover, an approximate 100-fold signal enhancement from nanosecond excitation (∼3 mJ/pulse, 10 ns duration) was observed as compared to femtosecond excitation (∼6 µJ/pulse, 90 fs duration).

Direct measurements of collisional Raman line broadening in the S-branch transitions of CO perturbed by CO, N2, and CO2.

We report direct measurement of collisional line-broadening coefficients associated with rotational Raman transitions of carbon monoxide (CO), obtained using time-resolved picosecond rotational coherent anti-Stokes Raman scattering spectroscopy. The dependencies of the CO self-broadening coefficients on rotational quantum number, J, and temperature are described for the J=3-16 lines of S-branch (ΔJ=+2) transitions for T=295-600 K at atmospheric pressure. Further, we report collisional linewidths of CO and collision partners N2 and CO2. The obtained S-branch linewidths of self-broadened CO agree well with previously reported frequency-domain experimental spectroscopy results, whereas the mixture-linewidth broadening coefficients differ from reported theoretical results by up to 80%.

Interference-free hybrid fs/ps vibrational CARS thermometry in high-pressure flames.

Interference-free hybrid femtosecond/picosecond vibrational coherent anti-Stokes Raman scattering (CARS) of nitrogen is reported for temperature measurements of 1300-2300 K in high-pressure, laminar H2-air and CH4-air diffusion flames up to 10 bar. Following coherent Raman excitation by 100 fs duration pump and Stokes pulses, a time-asymmetric probe pulse is used for the detection of spectrally resolved N2 CARS signals at probe delays as early as ∼200-300 fs. This allows for full rejection of nonresonant contributions while being independent of collisions for single-shot precision of ±2% at elevated pressures. The effects of collisions at longer probe-pulse delays are also investigated to determine the feasibility of varying the detection timing from 200 fs to 100 ps.

Mixture-fraction imaging at 1 kHz using femtosecond laser-induced fluorescence of krypton.

Femtosecond, two-photon-absorption laser-induced-fluorescence (TALIF) imaging measurements of krypton (Kr) are demonstrated to study mixing in gaseous flows. A measurement approach is presented in which observed Kr TALIF signals are 7 times stronger than the current state-of-the-art methodology. Fluorescence emission is compared for different gas pressures and excitation wavelengths, and the strongest fluorescence signals were observed when the excitation wavelength was tuned to 212.56 nm. Using this optimized excitation scheme, 1-kHz, single-laser-shot visualizations of unsteady flows and two-dimensional measurements of mixture fraction and scalar dissipation rate of a Kr-seeded jet are demonstrated.

Comparison of chirped-probe-pulse and hybrid femtosecond/picosecond coherent anti-Stokes Raman scattering for combustion thermometry.

A comparison is made between two ultrashort-pulse coherent anti-Stokes Raman scattering (CARS) thermometry techniques-hybrid femtosecond/picosecond (fs/ps) CARS and chirped-probe-pulse (CPP) fs-CARS-that have become standards for high-repetition-rate thermometry in the combustion diagnostics community. These two variants of fs-CARS differ only in the characteristics of the ps-duration probe pulse; in hybrid fs/ps CARS a spectrally narrow, time-asymmetric probe pulse is used, whereas a highly chirped, spectrally broad probe pulse is used in CPP fs-CARS. Temperature measurements were performed using both techniques in near-adiabatic flames in the temperature range 1600-2400 K and for probe time delays of 0-30 ps. Under these conditions, both techniques are shown to exhibit similar temperature measurement accuracies and precisions to previously reported values and to each other. However, it is observed that initial calibration fits to the spectrally broad CPP results require more fitting parameters and a more robust optimization algorithm and therefore significantly increased computational cost and complexity compared to the fitting of hybrid fs/ps CARS data. The optimized model parameters varied more for the CPP measurements than for the hybrid fs/ps measurements for different experimental conditions.

Seedless velocimetry at 100 kHz with picosecond-laser electronic-excitation tagging.

Picosecond-laser electronic-excitation tagging (PLEET), a seedless picosecond-laser-based velocimetry technique, is demonstrated in non-reactive flows at a repetition rate of 100 kHz with a 1064 nm, 100 ps burst-mode laser. The fluorescence lifetime of the PLEET signal was measured in nitrogen, and the laser heating effects were analyzed. PLEET experiments with a free jet of nitrogen show the ability to measure multi-point flow velocity fluctuations at a 100 kHz detection rate or higher. Both spectral and dynamic mode decomposition analyses of velocity on a Ma=0.8 free jet show two dominant Strouhal numbers around 0.24 and 0.48, respectively, well within the shear-layer flapping frequencies of the free jets. This technique increases the laser-tagging repetition rate for velocimetry to hundreds of kilohertz. PLEET is suitable for subsonic through supersonic laminar- and turbulent-flow velocity measurements.

Two-color vibrational, femtosecond, fully resonant electronically enhanced CARS (FREE-CARS) of gas-phase nitric oxide.

A resonantly enhanced, two-color, femtosecond time-resolved coherent anti-Stokes Raman scattering (CARS) approach is demonstrated and used to explore the nature of the frequency- and time-dependent signals produced by gas-phase nitric oxide (NO). Through careful selection of the input pulse wavelengths, this fully resonant electronically enhanced CARS (FREE-CARS) scheme allows rovibronic-state-resolved observation of time-dependent rovibrational wavepackets propagating on the vibrationally excited ground-state potential energy surface of this diatomic species. Despite the use of broadband, ultrafast time-resolved input pulses, high spectral resolution of gas-phase rovibronic transitions is observed in the FREE-CARS signal, dictated by the electronic dephasing timescales of these states. Analysis and computational simulation of the time-dependent spectra observed as a function of pump-Stokes and Stokes-probe delays provide insight into the rotationally resolved wavepacket motion observed on the excited-state and vibrationally excited ground-state potential energy surfaces of NO, respectively.

Selective two-photon absorptive resonance femtosecond-laser electronic-excitation tagging velocimetry.

Selective two-photon absorptive resonance femtosecond-laser electronic-excitation tagging (STARFLEET), a nonseeded ultrafast-laser-based velocimetry technique, is demonstrated in reactive and nonreactive flows. STARFLEET is pumped via a two-photon resonance in N2 using 202.25 nm 100 fs light. STARFLEET greatly reduces the per-pulse energy required (30 µJ/pulse) to generate the signature FLEET emission compared to the conventional FLEET technique (1.1 mJ/pulse). This reduction in laser energy results in less energy deposited in the flow, which allows for reduced flow perturbations (reactive and nonreactive), increased thermometric accuracy, and less severe damage to materials. Velocity measurements conducted in a free jet of N2 and in a premixed flame show good agreement with theoretical velocities, and further demonstrate the significantly less intrusive nature of STARFLEET.

Single-shot thermometry and OH detection via femtosecond fully resonant electronically enhanced CARS (FREE-CARS).

Femtosecond time-resolved, fully resonant electronically enhanced coherent anti-Stokes Raman scattering (FREE-CARS) spectroscopy, incorporating a two-color excitation scheme, is used to demonstrate selective and sensitive gas-phase detection of the hydroxyl (OH) radical in a reacting flow. Spectral resolution of the emitted FREE-CARS signal allows simultaneous detection of temperature and relative OH mole fraction under single-laser-shot conditions in a laminar ethylene-air flame. By comparison to previously reported OH concentration and temperature measurements, we demonstrate excellent single-shot temperature accuracies (∼2% deviation from adiabatic flame temperature) and precisions (∼2% standard deviation), with simultaneous relative OH concentration measurements that demonstrate high detection sensitivity (100-300 ppm).

Time- and frequency-dependent model of time-resolved coherent anti-Stokes Raman scattering (CARS) with a picosecond-duration probe pulse.

The hybrid femtosecond∕picosecond coherent anti-Stokes Raman scattering (fs∕ps CARS) technique presents a promising alternative to either fs time-resolved or ps frequency-resolved CARS in both gas-phase thermometry and condensed-phase excited-state dynamics applications. A theoretical description of time-dependent CARS is used to examine this recently developed probe technique, and quantitative comparisons of the full time-frequency evolution show excellent accuracy in predicting the experimental vibrational CARS spectra obtained for two model systems. The interrelated time- and frequency-domain spectral signatures of gas-phase species produced by hybrid fs∕ps CARS are explored with a focus on gas-phase N2 vibrational CARS, which is commonly used as a thermometric diagnostic of combusting flows. In particular, we discuss the merits of the simple top-hat spectral filter typically used to generate the ps-duration hybrid fs∕ps CARS probe pulse, including strong discrimination against non-resonant background that often contaminates CARS signal. It is further demonstrated, via comparison with vibrational CARS results on a time-evolving solvated organic chromophore, that this top-hat probe-pulse configuration can provide improved spectral resolution, although the degree of improvement depends on the dephasing timescales of the observed molecular modes and the duration and timing of the narrowband final pulse. Additionally, we discuss the virtues of a frequency-domain Lorentzian probe-pulse lineshape and its potential for improving the hybrid fs∕ps CARS technique as a diagnostic in high-pressure gas-phase thermometry applications.

Direct measurements of collisional Raman line broadening in the S-branch transitions of acetylene (C2H2).

We report direct measurements of the self- and N2-broadened Raman S-branch linewidths of acetylene (C2H2), obtained by employing time-resolved picosecond rotational coherent anti-Stokes Raman scattering spectroscopy. Using broadband 115-ps pump and Stokes pulses (~135 cm(-1) bandwidth) and a spectrally narrowed 90-ps probe pulse (~0.2 cm(-1) bandwidth), Raman-coherence lifetimes are measured at room temperature for the S-branch (ΔJ = +2) transitions associated with rotational quantum number J = 3-25. These directly measured Raman-coherence lifetimes, when converted to collisional linewidth broadening coefficients, differ from the previously reported broadening coefficients extracted from theoretical calculations by 6%-35% for self-broadening for C2H2 and by up to 60% for N2-broadened C2H2.

Direct measurements of collisionally broadened Raman linewidths of CO2 S-branch transitions.

We report direct measurements of S-branch Raman-coherence lifetimes of CO(2) resulting from CO(2)-CO(2) and CO(2)-N(2) collisions by employing time-resolved picosecond coherent anti-Stokes Raman scattering spectroscopy. The S-branch (ΔJ = +2) transitions of CO(2) with rotational quantum number J = 0-52 were simultaneously excited using a broadband (~5 nm) laser pulse with a full-width-at-half-maximum duration of ~115 ps. The coherence lifetimes of CO(2) for a pressure range of 0.05-1 atm were measured directly by probing the rotational coherence with a nearly transform-limited, 90-ps-long laser pulse. These directly measured Raman-coherence lifetimes, when converted to collisional linewidth broadening coefficients, differ from the previously reported broadening coefficients extracted from frequency-domain rotational Raman and infrared-absorption spectra and from theoretical calculations by 7%-25%.

Communication: hybrid femtosecond/picosecond rotational coherent anti-Stokes Raman scattering thermometry using a narrowband time-asymmetric probe pulse.

A narrowband, time-asymmetric probe pulse is introduced into the hybrid femtosecond/picosecond rotational coherent anti-Stokes Raman scattering (fs/ps RCARS) technique to provide accurate and precise single-shot, high-repetition-rate gas-phase thermometric measurements. This narrowband pulse-generated by inserting a Fabry-Pérot étalon into the probe-pulse beam path-enables frequency-domain detection of pure-rotational transitions. The unique time-asymmetric nature of this pulse, in turn, allows for detection of resonant Raman-active rotational transitions free of signal contamination by nonresonant four-wave-mixing processes while still allowing detection at short probe-pulse delays, where collisional dephasing processes are negligible. We demonstrate that this approach provides excellent single-shot thermometric accuracy (<1% error) and precision (~2.5%) in gas-phase environments.

Laser-induced fluorescence detection of hydroxyl (OH) radical by femtosecond excitation.

The development of a laser-induced fluorescence detection scheme for probing combustion-relevant species using a high-repetition-rate ultrafast laser is described. A femtosecond laser system with a 1 kHz repetition rate is used to induce fluorescence, following two-photon excitation (TPE), from hydroxyl (OH) radicals that are present in premixed laminar flames. The experimental TPE and one-photon fluorescence spectra resulting from broadband excitation into the (0,0) band of the OH A(2)∑(+)-X(2)Π system are compared to simulated spectra. Additionally, the effects of non-transform-limited femtosecond pulses on TPE efficiency is investigated.

Gas-phase thermometry using delayed-probe-pulse picosecond coherent anti-Stokes Raman scattering spectra of H2.

We report the development and application of a simple theoretical model for extracting temperatures from picosecond-laser-based coherent anti-Stokes Raman scattering (CARS) spectra of H2 obtained using time-delayed probe pulses. This approach addresses the challenges associated with the effects of rotational-level-dependent decay lifetimes on time-delayed probing for CARS thermometry. A simple procedure is presented for accurate temperature determination based on a Boltzmann distribution using delayed-probe-pulse vibrational CARS spectra of H2; this procedure requires measurement at only a select handful of probe-pulse delays and requires no assumptions about sample environment.

Hybrid femtosecond/picosecond coherent anti-Stokes Raman scattering for high-speed gas-phase thermometry.

We demonstrate hybrid femtosecond/picosecond (fs/ps) coherent anti-Stokes Raman scattering for high-speed thermometry in unsteady high-temperature flames, including successful comparisons with a time- and frequency-resolved theoretical model. After excitation of the N(2) vibrational manifold with 100 fs broadband pump and Stokes beams, the Raman coherence is probed using a frequency-narrowed 2.5 ps probe beam that is time delayed to suppress the nonresonant background by 2 orders of magnitude. Experimental spectra were obtained at 500 Hz in steady and pulsed H(2)-air flames and exhibit a temperature precision of 2.2% and an accuracy of 3.3% up to 2400 K. Strategies for real-time gas-phase thermometry in high-temperature flames are also discussed, along with implications for kilohertz-rate measurements in practical combustion systems.