Picosecond laser-induced fluorescence measurement of rotational energy transfer of OH A (2)?(+) (v? = 2) in atmospheric pressure flames

Rate constants for total and state-specific rotational energy transfer (RET) of OH A(2) ?(+) (v? = 2) have been measured directly in atmospheric methane-air and methane-oxygen flames for the first time to our knowledge. We used a picosecond Raman-excimer laser (tau(l) = 300 ps, lambda = 268 nm) to excite the P(11) (12.5) and Q(11) (16.5) A -X transitions in the (2, 0) band of OH molecules. We analyzed the resultant fluorescence with a high-resolution spectrometer in combination with a fast-gated, intensified CCD camera (tau(g) = 400 ps). We recorded the temporal evolution of the emission spectrum by shifting the detection time with respect to the laser pulse. Measured emission spectra were inverted to yield the time-dependent population of rotational levels in the excited state. We calculated rate constants for RET from the results of the fit. The total RET in v? = 2 is similar to v? = 0, 1. The state-specific rates are represented well by a simple energy-gap law.     

Thermally assisted fluorescence of laser-excited OH A(2)Σ(+) as a flame diagnostic tool

A simple laser-induced-fluorescence measurement technique for turbulent flame temperature and OH concentration measurement is proposed and successfully tested. The main idea is that a narrow-band tunable excimer laser beam (λ = 308 nm) is focused into a turbulent atmospheric-pressure nonpremixed flame. The OH molecule Q(1)(3) (X(2)II υ″ = 0, A(2)Σ+υ″ = 0) transition is excited. By subsequent vibrational energy transfer, the distribution in the molecules' upper electronic energy level (excited Σ(+) state) is redistributed. By evaluating the spectrum of the broadband emission from the υ' = 1 ? υ″ = 0 and υ' = 2 ? υ″ = 1 bands with a full spectral fit, we were able to evaluate the temperature and the OH molecule density. The concurrent processes of quenching, vibrational energy transfer, and rotational energy transfer were taken into account in the evaluation process. The results were compared with numerical flame calculations and revealed good agreement. One problem with this new proposed application of laser-induced fluorescence is the self-absorption of the emitted light. This, however, is shown not to be serious, but it has to be checked carefully. The main advantages are a simple experimental setup and procedure, high signal intensity, and a simple and straightforward data evaluation method. Thus this measurement technique is suitable for turbulent flame temperature and OH concentration measurement, and it is an alternative to other well-established techniques that are much more complicated.     

Investigation of OH X(2)II collisional kinetics in a flame using picosecond two-color resonant four-wave-mixing spectroscopy

Time-resolved two-color resonant four-wave-mixing spectroscopy was used to investigate collisions affecting the ground electronic state of the hydroxyl radical. Picosecond laser pulses provided adequate time resolution for measurements in an atmospheric-pressure methane-air flame. The grating spectroscopy technique used a combination of double resonance, time-delayed probing, and independent control of the polarization of each of the four fields involved in the wave-mixing process to enable measurement of the decay of laser-induced population, alignment, and orientation, as well as state-to-state transfer of these three moments. Results are presented for individual rotational levels of OH in X(2)II(3/2)(v=1).     

Picosecond investigation of the collisional deactivation of OH A 2Sigma+(v' = 1, N' = 4, 12) in an atmospheric-pressure flame

The collisional deactivation of the laser excited states A 2Sigma+(v' = 1, N' = 4, 12) of OH in a flame is studied by measurement of spectrally resolved fluorescence decays in the picosecond time domain. Quenching and depolarization rates, as well as vibrational energy-transfer (VET) and rotational energy-transfer (RET) rates are determined. An empirical model describes the temporal evolution of the quenching and VET rates that emerge from the rotational-state relaxation. Fitting this model to the measured 1-0 and 0-0 fluorescence decays yields the quenching and VET rates of the initially excited rotational state along with those that correspond to a rotationally equilibrated vibronic-state population. VET from the higher rotational state (N' = 12) shows a tendency for resonant transitions to energetic close-lying levels. RET is investigated by analysis of the temporal evolution of the 1-1 emission band. The observed RET is well described by the energy-corrected sudden-approximation theory in conjunction with a power-gap law.     

Detection of atomic hydrogen in flames using picosecond two-color two-photon-resonant six-wave-mixing spectroscopy

We report an investigation of two-color six-wave-mixing spectroscopy techniques using picosecond lasers for the detection of atomic hydrogen in an atmospheric-pressure hydrogen-air flame. An ultraviolet laser at 243 nm was two-photon-resonant with the 2S(1/2) <-- <-- 1S(1/2) transition, and a visible probe laser at 656 nm was resonant with H(alpha) transitions (n=3 <-- n=2). The signal dependence on the polarization of the pump laser was investigated for a two- beam polarization-spectroscopy experimental configuration and for a four- beam grating configuration. A direct comparison of the absolute signal and background levels in the two experimental geometries demonstrated a significant advantage to using the four-beam grating geometry over the simpler two-beam configuration. Picosecond laser pulses provided sufficient time resolution to investigate hydrogen collisions in the atmospheric-pressure flame. Time-resolved two-color laser-induced fluorescence was used to measure an n=2 population lifetime of 110 ps, and time-resolved two-color six-wave-mixing spectroscopy was used to measure a coherence lifetime of 76 ps. Based on the collisional time scale, we expect that the six-wave-mixing signal dependence on collisions is significantly reduced with picosecond laser pulses when compared to laser pulse durations on the nanosecond time scale.     

Crank-angle-resolved laser-induced fluorescence imaging of NO in a spark-ignition engine at 248 nm and correlations to flame front propagation and pressure release

Inside the combustion chamber of a spark-ignition engine, NO fluorescence is excited with a narrow-band tunable KrF excimer laser. The fluorescence light is detected by an intensified CCD camera that yields images of the NO distributions. Rotational-vibrational transitions of NO are excited by the A(2)Σ+ ? X(2)Π (0, 2) band system around 248 nm. Single laser shot planar NO distributions are obtained with good signal-to-noise ratio at all crank angles and allow us to locate areas of NO formation during combustion. The pressure within the combustion chamber is measured simultaneously with the NO distributions, which allows the evaluation of correlations between indicated work and NO formation. The crank-angle-resolved sequences of two-dimensional NO distributions and averaged pressure traces are presented for different engine-operating conditions. In addition, laser-induced predissociation fluorescence of OH excited by the same laser source is measured in order to visualize the corresponding flame front propagation and to compare the time of formation of NO relative to that of OH.     

Hydroxyl tagging velocimetry method optimization: signal intensity and spectroscopy

The previously demonstrated nonintrusive time-of-flight molecular velocity tagging method, hydroxyl tagging velocimetry (HTV), has shown the capability of operating both at room temperature and in flames. Well-characterized jets of either air (nonreacting cases) or hydrogen-air diffusion flames (reacting cases) are employed. A 7 x 7 OH line grid is generated first through the single-photon photodissociation of H2O by a approximately 193 nm pulsed narrowband ArF excimer laser and is subsequently revealed by a read laser sheet through fluorescence caused by A2sigma+(v' = 3) <-- X2pi(i)(v' = 0), A2sigma+(v' = 1) <-- X2pi(i)(v' = 0), or A2sigma+(v' = 0) < or = X2pi(i)(v' = 0) pumping at approximately 248, approximately 282, or approximately 308 nm, respectively. A detailed discussion of the spectroscopy and relative signal intensity of these various read techniques is presented, and the implications for optimal HTV performance are discussed.     

Lifetime measurements of several S, P, and D states of thallium in a glow discharge by single-step and two-step laser-excited fluorescence

The lifetimes of several states in a thallium see-through hollow cathode discharge, or galvatron, are obtained to characterize its potential as an atomic line filter. The lifetimes of the thallium 6(2)D(3/2), 6(2)D(5/2), and 7(2)S(1/2) states are measured by time-resolved single-step laser-excited fluorescence by use of a 276.787 nm laser pulse or a 535.046 nm laser pulse and measuring the resulting fluorescence waveform at the appropriate wavelength. Values of 6.4 +/- 0.1, 7.5 +/- 1.1, and 7.7 +/- 0.2 ns were obtained for the 6(2)D(3/2), 6(2)D(5/2), and 7(2)S(1/2) states, respectively, which agree with values obtained by previous authors, as well as calculated values. No current dependence was observed for each of these states. The lifetime of the long-lived thallium 6(2)P(3/2) degrees metastable state was measured by two-step laser-excited fluorescence at various applied currents. The metastable level was pumped by a 276.787 nm laser pulse, and a temporally delayed 535.046 nm laser pulse interrogated the population of the metastable state. Relating the fluorescence intensity to the population of the metastable state as a function of delay time yielded a decay curve for the 6(2)P(3/2) degrees metastable state. Values of 2.1 +/- 0.2, 2.8 +/- 0.1, 3.1 +/- 0.3, 3.8 +/- 0.4, and 4.8 +/- 0.6 micros were found for applied currents of 14.0, 12.0, 10.0, 8.0, and 6.0 mA, respectively. The resulting lifetimes for the 6(2)P(3/2) degrees metastable state clearly show a dependence on the applied current and are expected to be due to collisions with the wall of the cathode, as well as a contribution due to collisions with electrons.     

Picosecond planar laser-induced fluorescence measurements of OH A 2 + ( ' = 2) lifetime and energy transfer in atmospheric pressure flames

A picosecond, excimer-Raman laser (268 nm, 400 ps FWHM) was used for laser sheet excitation of OH in the (2, 0) band. The fluorescence was detected with a fast-gated, intensified camera (400-ps gate width). The effective collisional lifetime of the spectrally integrated fluorescence was measured in two dimensions by shifting the intensifier gate across the decay curve. The average lifetime is ~2.0 ns for a stoichiometric methane -air flame with spatial variations of +/-10 %. Shorter collisional lifetimes were measured for rich flame conditions that are due to a higher number density of the quenchers. Vibrational energy transfer (VET) was observed in premixed methane -air and methane -oxygen flames by putting the fast-gated camera behind a spectrometer. The spectrum of the methane -air flame shows strong VET in contrast with the methane -oxygen flame. This is because N2 is a weak electronic quencher but a strong VET agent. By fitting the measured time dependence of the different vibrational populations ( ' = 2, 1, 0) to a four-level model, rate constants for quenching and VET were determined. For the lower states ( ' = 0, 1) our results are in good agreement with literature values. For a prediction of a spectrally integrated, collisional lifetime in a known collisional environment it is important to consider not only the quenching but also the amount of energy transfer in the excited state as well as the spectral detection sensitivity.     

Experimental investigation of saturated degenerate four-wave mixing for quantitative concentration measurements

Degenerate four-wave mixing (DFWM) line shapes and signal intensities are measured experimentally in well-characterized hydrogen-air flames operated over a wide range of equivalence ratios. We use both low (perturbative) and high (saturating) beam intensities in the phase-conjugate geometry. Resonances in the A 2Sigma+ -X 2II (0,0) band of OH are probed with multiaxial-mode laser radiation. The effects of saturation on the line-center signal intensity and the resonance linewidth are investigated. The DFWM signal intensities are used to measure OH number densities in a series of near-adiabatic flames at equivalence ratios ranging from 0.5 to 1.5. Use of saturating pump intensities minimizes the effects of beam absorption, providing more-accurate number density measurements. The saturated DFWM results are in excellent agreement with OH absorption measurements and equilibrium calculations of OH number density. The polarization dependence of the P(1)(2) and R(2)(1) resonances is investigated in both laser intensity regimes. There is a significant change in relative reflectivities for different polarization configurations when saturated.     

Fluorescence feedback control of an active Q-switched diode-pumped Nd:YVO4 laser

We have implemented active feedback control in a Q-switched diode-pumped Nd:YVO(4) laser by monitoring the fluorescence intensity from the laser crystal. When the initial inversion level indicated by the detected fluorescence has reached a predetermined value, Q switching is initiated. This scheme allowed us to vary the reproducibility of the output pulse peak power and pulse width. The novel active Q-switching approach can reduce the shot-to-shot variations of the output pulse peak power and the pulse width.     

Enhanced photoluminescence decay processes of doped CaS phosphors at low temperature

CaS phosphor samples singly doped with Mn impurity and doubly doped with Mn and X (X=?Fe, Co and Ni) have been synthesized using a flux method. Crystal structure and phase identification of doped CaS phosphors have been carried out by X-ray diffraction (XRD) studies. A pulse excitation method has been employed to study the optical parameters of the doped phosphors. Excited state lifetime measurements at liquid nitrogen temperature were carried out with a pulsed UV laser (nitrogen laser) as the excitation source has a short pulse width (10?ns) and high peak power (200?kW per pulse). The results have been compared with room temperature lifetime studies. Enhancement in photoluminescence intensity and lifetime shortening in these synthesized doped phosphors is reported at low temperature. The lifetime values have been found to be in the microsecond time domain for CaS:Mn phosphors while on addition of a quencher impurity Ni to CaS:Mn phosphors, the lifetime values reduce to the nanosecond time domain at 77?K temperature. A thermally activated carrier transfer model has been proposed to explain the observed abnormal temperature behaviour of emission from CaS:Mn, X-doped phosphors.     

Application of quantitative two-line OH planar laser-induced fluorescence for temporally resolved planar thermometry in reacting flows

A temporally resolved approach for measurement of two-dimensional temperature fields in reacting flows is experimentally investigated. The method, based on planar laser-induced fluorescence of the hydroxyl (OH) radical, is applicable in many combustion environments, including variable density flow fields. As a means of examining the accuracy of the technique, temperature images, from 1300 to 3000 K and 0.4 to 3 atm, have been acquired in shock-heated H(2)-O(2)-Ar flows with a two-laser, two-image ratio scheme. A complete measurement system for producing accurate, effectively instantaneous temperature images is described; the system includes single-shot monitors for laser-sheet energy distributions and spectral profiles. Temperature images obtained with the OH A(2)Σ(+) ? X(2)II (1, 0) P(1)(7)-Q(2)(11) transition pair exhibit a systematic error of only 7% over the entire range of conditions, with the error most likely dominated by shot-to-shot fluctuations in the lasers'spectral profiles. The largest error source in the instantaneous temperature images is photon shot noise. A group of OH transition pairs that provide good temperature sensitivity and strong signals for reduced shot-noise error over a range of flow-field conditions is also presented.     

Phase-locked two-line OH planar laser-induced fluorescence thermometry in a pulsating gas turbine model combustor at atmospheric pressure

Two-line OH planar laser-induced fluorescence (PLIF) thermometry was applied to a swirling CH4/air flame in a gas turbine (GT) model combustor at atmospheric pressure, which exhibited self-excited combustion instability. The potential and limitations of the method are discussed with respect to applications in GT-like flames. A major drawback of using OH as a temperature indicator is that no temperature information can be obtained from regions where OH radicals are missing or present in insufficient concentration. The resulting bias in the average temperature is addressed and quantified for one operating condition by a comparison with results from laser Raman measurements applied in the same flame. Care was taken to minimize saturation effects by decreasing the spectral laser power density to a minimum while keeping an acceptable spatial resolution and signal-to-noise ratio. In order to correct for the influence of laser light attenuation, absorption measurements were performed on a single-shot basis and a correction procedure was applied. The accuracy was determined to 4%-7% depending on the location within the flame and on the temperature level. A GT model combustor with an optical combustion chamber is described, and phase-locked 2D temperature distributions from a pulsating flame are presented. The temperature variations during an oscillation cycle are specified, and the general flame behavior is described. Our main goals are the evaluation of the OH PLIF thermometry and the characterization of a pulsating GT-like flame.     

Theory of Optical Two-photon Rotary Echo

We present a theory of optical two-photon rotary echo for the case when the direct couplings between the three levels due to spontaneous decay to and from the intermediate state dominate the indirect couplings (collisional, etc.) to the passive levels and the phase-interrupting (P.I.) collisions cannot be ignored. For this situation which generally obtains in the visible/U.V. region which is relevant for many two-photon transient experiments, the ‘two-photon Bloch equations’ with non-resonant intermediate state are non-trivially different from the familiar (two-level) Bloch equations with or without direct coupling. An explicit analytical calculation demonstrates two-photon rotary echo with the usual dependence on the total phase shift. The dependence of the echo peak on pulse delay time is governed by a damping constant in which ‘intensity modification’ involves only the P.I. collision constant and not the spontaneous decay constant in sharp contrast to the one-photon case. For the case of counter-propagating beams, the intensity modified echo damping constant turns out to be especially simple. We suggest that the features unique to the two-photon rotary echo can be usefully exploited for the empirical determination of the polarization decay constant.     

Imaging of trace species distributions by degenerate four-wave mixing: diffraction effects, spatial resolution, and image referencing

We describe the theory of imaging by degenerate four-wave mixing (DFWM) using a standard diffraction theory of imaging by coherent light. We demonstrate that, even with the phase-conjugating geometry, no aberration correction can be achieved by DFWM imaging. We demonstrate the coherent nature of DFWM image formation using spatially modulated signals generated in flame OH in the phase-conjugating geometry. The intensity distribution in the Fourier plane of a telecentric lens system is shown to be the spatial Fourier transform of the object distribution characteristic of coherent imaging. The brightness of the DFWM signals exceeds that of similar laser-induced fluorescence signals that can be discriminated by restricting the aperture of the imaging system while still allowing a spatial resolution of approximately 70 ?m. DFWM imaging with the forward-folded boxcars geometry is demonstrated and used in a simple referencing scheme to compensate for structure on the images imposed by nonuniformity of the laser beams employed. Images formed in NO are used to illustrate that structure on a scale of less than 100 ?m arising from beam inhomogeneity can be removed by this referencing technique.     

High bandwidth underwater optical communication

We report error-free underwater optical transmission measurements at 1 Gbit/s (10(9) bits/s) over a 2 m path in a laboratory water pipe with up to 36 dB of extinction. The source at 532 nm was derived from a 1064 nm continuous-wave laser diode that was intensity modulated, amplified, and frequency doubled in periodically poled lithium niobate. Measurements were made over a range of extinction by the addition of a Mg(OH)(2) and Al(OH)(3) suspension to the water path, and we were not able to observe any evidence of temporal pulse broadening. Results of Monte Carlo simulations over ocean water paths of several tens of meters indicate that optical communication data rates >1 Gbit/s can be supported and are compatible with high-capacity data transfer applications that require no physical contact.     

Flame flow tagging velocimetry with 193-nm H2O photodissociation

In a new nonintrusive, instantaneous flow tagging method called hydroxyl tagging velocimetry (HTV), a molecular grid of hydroxyl (OH) radicals is written into a flame and the displaced grid is imaged at a later time to give the flame's velocity profile. Single-photon photodissociation of vibrationally excited H(2)O, when a 193-nm ArF excimer laser is used, produces a tag line of superequilibrium OH and H photoproducts in a high-temperature flow field that itself may contain ambient OH. The tag line OH concentration is composed mostly of direct OH photoproducts, but OH is also indirectly produced through H photoproduct reactions with oxygen-bearing species. For lean and modestly rich flames the OH tag lifetime is of the order of 1 ms. For very rich H(2)-air flames (equivalence ratio of 4.4) the lifetime drops to 200 ns. After displacement the position of the OH tag line is revealed through fluorescence caused by OH (A-X) (3 <-- 0) excitation by using a 248-nm tunable KrF excimer laser. A HTV grid of multiple tag lines, providing multipoint velocity information, is experimentally demonstrated in a turbulent H(2)/N(2)-air diffusion flame.     

Temperature imaging in a supersonic free jet of combustion gases with two-line OH fluorescence

Temperature measurements were performed in a shock-tunnel-generated free jet of hydrogen/oxygen reaction products diluted in argon with a nonsimultaneous, two-excitation-line planar laser-induced fluorescence technique with the hydroxyl radical (OH) as a tracer. Single-shot images were obtained with broadband excitation of isolated transitions in the A(2)Σ(+) ? X(2)Π(1, 0) band of OH near 282 nm, with broadband, temporally integrated detection of the resulting nonresonant emission. A measurement of the fluorescence lifetime in the free jet showed no variation with excited rotational level, allowing the rotational temperature to be obtained from the ratio of single-shot images with laser excitation of different rovibronic transitions.     

Self-focusing and frequency broadening of an intense short-pulse laser in plasmas.

An intense ultrafast laser pulse propagating through a plasma undergoes self-focusing and self-phase-modulation as a result of relativistic mass nonlinearity. The inclusion of a quartic (r4) term in the expansion of the eikonal in the radial coordinate r allows the modification of the shape of the radial intensity profile. The front of the pulse, under the combined effects of time-dependent self-focusing and frequency downshifting, acquires a severely distorted temporal shape. The radial profile for I(lambda)2(mu) < 2.8 x 1018 W/cm2, where I is the axial laser intensity and lambda(mu), is the laser wavelength in micrometers, is transformed from a Gaussian to a super-Gaussian because of the faster convergence of the marginal rays than the paraxial rays. In the opposite case of I(lambda)(2)(mu) > 2.8 x 10(18) W/cm2 when nonlinear plasma permittivity approaches saturation, the radial profile in the axial region becomes broader than the Gaussian.