S-branch N(2)-H(2) Raman linewidths have been measured in the temperature region 294-1466 K using time-resolved dual-broadband picosecond pure rotational coherent anti-Stokes Raman spectroscopy (RCARS). Data are extracted by mapping the dephasing rates of the CARS signal temporal decay. The J-dependent coherence decays are detected in the time domain by following the individual spectral lines as a function of probe delay. The linewidth data set was employed in spectral fits of N(2) RCARS spectra recorded in binary mixtures of N(2) and H(2) at calibrated temperature conditions up to 661 K using a standard nanosecond RCARS setup. In this region, the set shows a deviation of less than 2% in comparison with thermocouples. The results provide useful knowledge for the applicability of N(2) CARS thermometry on the fuel-side of H(2) diffusion flames.

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.

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.

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.

We review three photofragmentation detection approaches, describing the detection of (1) vapor-phase mercuric chloride by photofragment emission, (2) vapor-phase nitro-containing compounds by photofragmentation-ionization, and (3) surface-bound organophosphonate compounds by photofragmentation-laser-induced fluorescence.

We demonstrate detection of nitro-containing compounds with laser photofragmentation (PF) coupled with resonance enhanced multiphoton ionization (REMPI) and ion mobility spectrometry (IMS). In PF-REMPI, a laser dissociates the parent molecules, producing fragments that can then be ionized by absorption of additional laser photons. The production of these ions strongly depends on the wavelength of laser light, with ion yields corresponding to the absorption spectrum of the fragments [nitric oxide (NO) in the present case]. Combining IMS with PF-REMPI provides further specificity, separating ions according to their mobilities through an atmospheric-pressure drift tube. In this work, we use a pulsed UV laser to examine the characteristics of atmospheric-pressure PF-REMPI, the chemistry occurring in the ionization region and drift tube, and the viability of detecting ions created by both resonance-enhanced and nonresonant ionization. Probing NO in a helium-nitrogen bath, we demonstrate that the detection of ions displays single-shot response to changes in ion generation, with an ion extraction-to-collection efficiency of approximately 12%. We then evaluate the sensitivity and specificity of PF-REMPI/IMS as applied to the detection of both the explosive surrogate 2, 4-dinitrotoluene and the nuisance compound nitrobenzene.

Time-resolved picosecond pure-rotational coherent anti-Stokes Raman spectroscopy is applied for thermometry and 1-D imaging in flames. Time-delaying the probe pulse enables successful suppression of unwanted resonant and non-resonant four wave mixing background signals.

In this work we characterize time-resolved pure-rotational CARS using picosecond lasers in combination with data acquisition and evaluation in the frequency-domain. By delaying the probe pulse relative to the pump and Stokes pulses typical drawback of nanosecond pure rotational CARS are prevailed. The results from measurements in a laminar sooting nonpremixed propane flame are compared with those obtained using the commonly applied CARS polarization technique for interference suppression.

The common misconception that hydrogen flames are not visible is examined. Examples are presented of clearly visible emissions from typical hydrogen flames. It is shown that while visible emissions from these flames are considerably weaker than those from comparable hydrocarbon flames, they are indeed visible, albeit at reduced light levels in most cases. Detailed flame spectra are presented to characterize flame emission bands in the ultraviolet, visible and infrared regions of the spectrum that result in a visible hydrogen flame. The visible blue emission is emphasized, and recorded spectra indicate that fine spectral structure is superimposed on a broadband continuum extending from the ultraviolet into the visible region. Tests were performed to show that this emission does not arise from carbon or nitrogen chemistry resulting from carbon-containing impurities (hydrocarbons) in the hydrogen fuel or from CO2 or N2 entrainment from the surrounding air. The spectral structure, however, is also observed in methane flames. The magnitude of the broadband emission increases with flame temperature in a highly nonlinear manner while the finer spectral structure is insensitive to temperature. A comparison of diffusion and premixed H2 flames shows that the fine scale structure is comparable in both flames.

Improved measurements of the radiative lifetimes of NO A (2)Sigma(+)(v' = 0,1,2) are presented and used to update the absolute electronic transition moment for the NO gamma bands. The pressure-dependent fluorescence decay rate was measured in a low-pressure, room-temperature, flow cell containing dilute mixtures of NO in N-2 using time-resolved laser-induced fluorescence excited with a picosecond laser and detected with a microchannel-plate photomultiplier tube. Fluorescence decay rates were determined using an analysis procedure that accounted for the electronic response of the detection system and measurement noise. Radiative lifetimes were determined from an extrapolation of the measured decay rates to zero pressure. In comparison with prior measurements of these radiative lifetimes, the improved experimental approach and analysis procedure result in a significant improvement in the measurement precision. The accuracy of the fluorescence decay-rate measurements was confirmed by independent measurements using time-correlated single-photon counting and time-resolved probing of laser-excited population in A (2)Sigma(+) using 266 nm photoionization and charge detection. The measured radiative lifetimes are 192.6 +/- 0.2 ns for v' = 0, 186.2 +/- 0.4 ns for v' = 1, and 179.4 +/- 0.7 ns for v' = 2. The measured lifetimes are shown to be in outstanding agreement with those predicted by an electronic transition moment that is identical in form to the function recommended by Luque and Crosley [J. Chem. Phys. 111, 7405 (1999)] after appropriate rescaling. This rescaling does not affect the agreement of the transition moment function with the previously reported vibrational branching ratios and improves agreement with previously reported absolute oscillator strength measurements. Based on the rescaled transition moment, updated values of absolute transition probabilities in the NO A (2)Sigma(+)-X (2)Pi system are presented. (C) 2009 American Institute of Physics. [doi:10.1063/1.3227520]

The effects of collisional-energy-transfer and dephasing rates on ERE-CARS in nitric oxide are investigated. A parametric study of the effects of collisions on the ERE-CARS signal demonstrates a reduced collisional dependence for saturating laser fields.

Interference-free, two-photon-excited planar laser-induced fluorescence (PLIF) imaging of atomic hydrogen is demonstrated in steady premixed methane flames. PLIF measurements of atomic hydrogen present a challenge because of the relatively weak two-photon absorption cross-sections and the nonlinear dependence of the laser-induced fluorescence (LIF) signal on laser intensity. Previous two-photon LIF measurements of atomic hydrogen in hydrocarbon flames using nanosecond laser excitation have identified complications from photolytic production of hydrogen atoms by the excitation laser. Recent results from line-imaging studies in our laboratory indicate a significant advantage to using picosecond excitation for imaging atomic hydrogen with negligible photolytic interference. In the current study, we extend our capabilities for interference-free PLIF imaging of atomic hydrogen in steady premixed CH4/O2/N2 flames. Peak single-shot signal-to-noise ratios of approximately 6–8 are achieved, and the estimated single-shot detection limit is on the order of 1016cm-3. Avoidance of interference and stimulated emission and the effects of fluorescence quenching are discussed. Averaged composite PLIF images are generated by combining images from multiple axial locations in the flame. The images show enhanced number densities of atomic hydrogen near the flame tip, in accordance with numerical predictions of diffusional focusing of H-atoms resulting from the sharp curvature of the flame front.

Two-color resonant four-wave mixing (TC-RFWM) is advertised as a unique spectroscopic device, enabling direct time-resolved measurement of the collisional state-to-state transfer characteristics (rates and correlation times). These characteristics are phase-sensitive and open wider opportunities to study the rotational relaxation processes. Further perspectives are offered by the recently recorded collision-induced picosecond TC-RFWM signals of OH. Their quantitative interpretation is now under development. Copyright (C) 2009 John Wiley & Sons, Ltd.

A six-level model is developed and used to study the effects of collisional energy transfer and dephasing on electronic-resonance-enhanced coherent anti-Stokes Raman scattering (ERE-CARS) in nitric oxide. The model includes the three levels that are coherently coupled by the three applied lasers as well as three additional bath levels that enable inclusion of the effects of electronic quenching and rotational energy transfer. The density-matrix equations that describe the evolution of the relevant populations and coherences are presented. The parametric dependencies of the ERE-CARS signal on collisional energy transfer and dephasing processes are described in terms of both a steady-state analytical solution and the numerical solutions to the governing equations. In the weak-field limit, the ERE-CARS signal scales inversely with the square of the dephasing rates for the electronic and Raman coherences. In accord with published experimental observations [Roy et al., Appl. Phys. Lett. 89, 104105 (2006)], the ERE-CARS signal is shown to be insensitive to the collisional quenching rate. Parametric dependencies on quenching, rotational energy transfer, and pure electronic dephasing are presented, demonstrating reduced collisional dependence for saturating laser fields.

We investigate the 205-nm photolytic production of atomic hydrogen in methane flames. This process represents a significant interference in two-photon, laser induced-fluorescence (TP-LIF) detection of atomic hydrogen in flames. Relative TP-LIF profiles of the photolytically produced H atoms were measured using a pump-probe technique in atmospheric-pressure, premixed CH 4 /O 2 /N 2 flames. A high-fluence, non-resonant, nanosecond pump laser created H atoms by photodissociating flame constituents, and a copropagating, non-perturbing picosecond laser probed the photolytically produced Hatoms via TP-LIF. Spatial profiles of photolytically produced H atoms indicate that both intermediate and product species contribute to the interference in all flames. Excellent agreement between simulated and measured interference signals is observed in the product region of the flames. Vibrationally excited H 2 O is the dominant source of interference in the product region, but an additional contribution is attributed to vibrationally excited OH radicals. In the flame-front region, CH 3 is the dominant precursor, and photodissociation of C 2 H 2 becomes increasingly important in rich flames. Mechanisms for sequential photodissociation of CH 3 and C 2 H 2 are presented, indicating that complete dissociation at 205 nm of both precursors is feasible.