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     

Thermometry of an oxy-acetylene flame using multiplex degenerate four-wave mixing of C2

Thermometry of an oxy-acetylene flame using multiplex Degenerate Four-Wave Mixing (DFWM) of C₂ is demonstrated. More than 100 rotational transitions in thed ³ _g a ³ _u (0,0) Swan band of C₂ could be recorded simultaneously by use of a pulsed, broad bandwidth modeless laser. Temperatures were inferred by fitting temperature-dependent synthetic spectra of single- or multiple-shot averaged spectra. The strength and reliability of recorded signals together with the large number of rotational lines observed suggest that multiplex DFWM is a promising technique for minor species detection and for temporally resolved temperature measurements in luminous environments. Factors influencing the accuracy and precision of single-shot thermometry using the technique are discussed.     

An experimental and kinetic modeling study of a premixed nitromethane flame at low pressure

A premixed nitromethane/oxygen/argon flame at low pressure (4.67 kPa) has been investigated using tunable vacuum ultraviolet (VUV) photoionization and molecular-beam mass spectrometry. About 30 flame species including hydrocarbons, oxygenated and nitrogenous intermediates have been identified by measurements of photoionization efficiency spectra. Mole fraction profiles of the flame species have been determined by scanning burner position at some selected photon energies. The results indicate that N₂ and NO are the major nitrogenous products in the nitromethane flame. Compared with previous studies on nitromethane combustion, a number of unreported intermediates, including C₃H₄, C₄H₆, C₄H₈, C₂H₂O, C₂H₄O, CH₃CN, H₂CNHO, C₃H₃N and C₃H₇N, are observed in this work. Based on our experimental results and previous modeling studies, a detailed oxidation mechanism including 69 species and 314 reactions has been developed to simulate the flame structure. Despite some small discrepancies, the predictions by the modeling study are in reasonable agreement with the experimental results.     

The effects of collisional quenching on degenerate four-wave mixing

We report a theoretical and experimental investigation of the effects of collisional quenching on resonant degenerate four-wave mixing (DFWM). Using single-mode laser radiation, peak signal intensity measurements were performed on an isolated line in the A – X transition of NO. By using appropriate mixtures of N₂ and CO₂ as buffer gases, we varied the collisional quenching rate over several orders of magnitude while maintaining a fixed total collisional dephasing rate. The mixtures had approximately 100 Torr total pressure and were at room temperature. For I/I _sat approximately equal to 0.02, DFWM intensities were found to be less affected by variations in quench rate than were laser-induced fluorescence (LIF) intensities (I and I _sat are the pump laser and one-photon saturation intensities, respectively). Moreover, for I/I _sat roughly equal to 0.5, DFWM intensities were observed to be nearly independent of quench rate. The results are compared to two theoretical predictions, with good agreement observed. Both theories indicate that the minimum sensitivity of DFWM to quenching occurs near I/I _sat1.     

The effect of the relative position of the bandgap with respect to laser wavelength on the behaviour of DFWM in semiconductor-doped glasses

Degenerated four-wave mixing (DFWM) was realised in five commercial semiconductor-doped glasses (Corning CS3–66, CS3–67, CS3–68, CS3–69, CS3–70). The reflectivity obtained for each glass seems very dependent on the energy excess (E=hv–E _g) and relatively independant on l, the product of the absorption coefficient () by the sample thickness (l). The decay time of the DFWM signal was measured for each glass. The relaxation was found to be different when the photon energy is under or over the gap.     

Mössbauer spectroscopic studies of (n-C n H2n +1NH3)2SnX6 (n=0-4; X = Cl or Br) and their related complexes

Complexes of the type (n-C _n H_2n +1NH₃)₂SnX₆ (0n 4 and X=Cl or Br) have been investigated with a variety of physico-chemical techniques. The structural phase transitions were found in some of these complexes. The temperature dependence of the Mössbauer spectral absorption area for (C₂H₅NH₃)₂SnCl₆ and (C₂H₅NH₃)₂SnBr₆ changed sharply at phase transition temperatures. The temperature dependences for (n-C₄H₉NH₃)₂SnCl₆ and (n-C₄H₉NH₃)₂SnBr₆ decreased gradually with an increase in temperature. The correlation between the temperature dependence of the spectral absorption area and the motion of n-C _n H_2n+1NH₃ ⁺ ions is discussed.     

CARS spectroscopy of molecules and clusters in supersonic jets

Supersonic molecular beams of D₂, CH₄, NH₃, and C₂H₄ are investigated in the expansion region employing collinear coherent anti-Stokes Raman spectroscopy (CARS). The analysis of rotationally resolved CARS spectra allows the determination of temperatures in the beam. The rotational relaxation as a function of stagnation pressure and separation from the nozzle is studied by recording theQ branch for D₂ and the ₃ R andS branches for CH₄. Rotational temperatures for NH₃ are determined by investigating the complete ₃ band. At strong stagnation conditions broad structures arise which can be attributed to the formation of NH₃ clusters. For C₂H₄ the ₅ band with resolved rotational structure is reported. Again, at larger distances from the nozzle, broad structures are observed. They are assigned to the ₁ and ₅ vibrations in the C₂H₄ cluster.     

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     

Degenerate four-wave-mixing spectroscopy in NaH

We performed DFWM spectroscopy on X ^–1+–A ¹⁺ transitions in NaH produced in an indirect photochemical reaction between Na(3p) and H₂ and detected v=1, 2 and 3 ground state vibrational levels of NaH molecules, whereas with resonance enhanced CARS, we observed v=0 levels only. This different sensitivity can be explained by considering the Franck-Condon-factors and the relevant damping coefficients for the corresponding transitions in the NaH molecule. Time resolved DFWM spectroscopy showed that NaH(v=1) molecules effectively live much longer than Na(3p) atoms which merely follow the laser excitation pulse.     

Laser-ionization mass-spectrometric studies on laser ablation of a nitrogen-rich polymer at 532 nm and 1064 nm

Laser-ionization Time-Of-Flight (TOF) mass-spectrometric studies have been carried out on the 532 nm and 1064 nm laser ablation products from a nitrogen-rich polymer. The polymer used had an elemental composition of C_6.0N_8.9H_3.4 and consisted of C=N, C-N, and N-H chemical bonds. The TOF mass spectra observed were composed of various peaks (150 amu) depending on the ablation laser wavelength. The primary peaks were assigned to C⁺, CN⁺, CHnN⁺ ₂ (n=1–3) and C₂H₂N⁺ ₃ for 532 nm ablation, and C⁺, C⁺ ₃, HCN⁺, HCCN⁺, CH₂NH⁺, HNCN⁺, H₃NCN⁺, and C₄H₄N⁺ ₇ for 1064 nm ablation. The flight velocity distributions with peak velocities ranging from 8.6×10³ cm/s to 3.8×10⁴ cm/s were measured for these products. The distinct velocity distributions observed between small and large products indicate the presence of two origins in the fragment ejection process from the polymer for both 532 nm and 1064 nm ablation. Furthermore, we suggest an importance of the translational energy of the fragments for the product generation in the laser plume.     

Rotational and vibrational temperature determination by DFWM spectroscopy

Using the DFWM technique we determined rotational and vibrational temperatures of NaH molecules in a dynamical system consisting of NaH, Na, H and H₂ for several heat-pipe oven temperatures. We applied a new way to determine the dependence of the DFWM signalI _c ^int on the power of the transition dipole momentµ without previous knowledge of the temperature. The revealed dependence isI _c ^int µ ⁴. In this case the laser intensities were found to be of the same order as the saturation intensity in accordance with simple DFWM theory. A usual Boltzmann plot was employed for the determination of the relevant rotational temperatures, which displayed higher values than the oven temperature.     

Temperature measurement using degenerate four-wave mixing with non-saturating laser powers

We report the use of Degenerate Four-Wave Mixing (DFWM) in the OHA ^{2 +} X ² ( = 0 = 0) band for temperature determination in a propane/air flame using laser powers below the saturation level. We show that at these low power levels the dependence of the signal on the dipole moment for the transition has to be established before meaningful temperature data can be obtained. This presents a paradox in that the temperature has to be known before the form of the dependence on the dipole moment can be determined. Solutions to this paradox are presented. We also show that absorption of the laser beams in this OH band system cannot be neglected and that failure to correctly account for the absorption leads to a large over estimate of the flame temperature. Furthermore, we show that the accuracy of the absorption-corrected temperature is critically dependent on the accuracy with which the measurement position within the flame is known. Finally, the temperature calculated from DFWM spectra using the correct dipole moment power and absorption is compared to the temperatures obtained using Laser-Induced Fluorescence (LIF) and Coherent Anti-Stokes Raman Spectroscopy (CARS).     

Resonant pumping far-infrared NH3 laser

A far-infrared (FIR) NH₃ laser was resonantly pumped with a line-tunable infrared (IR) NH₃ laser. The number of the observed FIR laser lines amounted to 33. Most of them belonged toaR(J,K) rotation-inversion transition in (0, 1, 0, 0) vibrational state. The line tunability of sealed-off FIR NH₃ laser was almost achieved in 90, 115, 150, and 220 m wavelength regions by the selective line tuning of the pumping IR NH₃ laser.     

Anisotropy of the nonlinear optical susceptibility χ(3) in polydiacetylene single crystals

The anisotropy of ⁽³⁾ in Poly-bis(p-Toluene Sulfonate) of 2.4-hexadiyne-1.6-diol (PTS) PolyDiAcetylene (PDA) single crystals is investigated by Degenerate Four-Wave Mixing (DFWM) at a wavelength of 720 nm. The symmetries of ⁽³⁾(–;, –,) identify the non-vanishing and independent components of the tensor. For the calculation of the ⁽³⁾ elements from the measured values, the anisotropy of both the linear optical index of refraction and the absorption coefficient is included in the coupled wave approach. A magnitude of 10^–10 esu is measured for the ⁽³⁾ component if all beam polarizations are parallel to the polymer chains. The least upper bound for all other measurable components is estimated to be 10^–12 esu. The results for the intensity dependence of the DFWM signal are explained in terms of a thermooptic effect. Measurements on the orientational dependence of the DFWM signal in the samples are carried out, and the influence of the anisotropy of the linear optical parameters on the measured curves is discussed. A method for the preparation of thin layered polymer single crystals of poly-bis (4-ButoxyCarbonyle-Methylene-Urethane) of 4.6-decadiyne-1.1-diol (4-BCMU) and the first DFWM measurements on these samples are presented.     

Laser-induced fluorescence detection of singlet CH2 in low-pressure methane/oxygen flames

Methylene, CH₂, is a chemically important intermediate in hydrocarbon combustion but has previously eluded optical detection in a combustion environment. The CH₂ signal as a function of height above the burner surface in a premixed, laminar, methane/oxygen flame (5.6 Torr and fuel equivalence ratio 1.05) is measured by laser-induced fluorescence (LIF) in the B ₁ – ã¹ A ₁ electronic system. The ã state which lies 3165 cm^–1 above the ground state is populated at the high temperatures of the flame (800–1800 K). Although less than one photon for each laser pulse is detected, we can unambiguously attribute the LIF features in the region 450 to 650 nm to CH₂ by both scanning the excitation laser and dispersing fluorescence. LIF temperatures and CH and OH LIF concentration profiles are also obtained for the flame. The CH₂ radical concentration maximum occurs closer to the burner than that of either OH or CH, as expected from models of methane combustion chemistry.     

Optically pumped submillimetre laser action in formaldoxime and ammonia

Strong submillimetre laser action has been obtained on five lines of a new laser gas, formaldoxime. Several new emission lines have also been produced by isotopic CO₂ laser pumping of¹⁴NH₃ and¹⁵NH₃. One of these lines at 102.9 m is a rotation-inversion transition in the 2v ₂ state, and is the first example of cw laser action in such a highly excited state.     

Efficient optically pumped NH3 amplifiers in the 10–12 μm region

A pulsed transversely excited CO₂ laser operating on the 9R(30) transition is used to optically pump mixtures of NH₃ in buffer gas. A simple oscillator/amplifier system characterizes the performance of the NH₃ amplifier in the 11 m region. Small-signal gain coefficients of >10%/cm measured on the aQ(3,3) transition at 10.7 m, while pump conversion efficiencies of 50% are shown to occur under saturation conditions. The NH₃ laser system is described by a rate-equation model, which is validated by comparison with experiment over a wide range of operating conditions. Measurements are made for NH₃ concentrations ranging from 0.05 to 0.2%, with Ar, N₂, and He buffer gas pressures from 170 to 700 Torr, and for gas temperatures from 200 to 300 K. Optically pumped NH₃ is shown to be a versatile and efficient system for the amplification of mid-infrared radiation.     

Two-photon predissociative fluorescence of H2O by a KrF laser for concentration and temperature measurement in flames

Two-photon laser-induced predissociative fluorescence (LIPF) of H₂O is examined as a potential measurement technique of H₂O concentration and temperature in flames. Two-photons of 248 nm light from a narrowband KrF laser excite H₂O to the highly predissociative state in a hydrogen-air flame. The subsequent bound-free emission is observed from 400–500 nm in the flame at temperatures of 1000–2000 K and is found to be free of fluorescence interference from other flame species. This LIPF signal is not affected by collisional quenching due to the short lifetime of the predissociative state (2.5 ps). Broadband laser dispersion spectra, narrowband laser dispersion spectra, laser excitation spectra and probability density functions of the H₂O fluorescence are obtained in the hydrogen flame. The H₂O LIPF signal is found to be temperature sensitive and a two-line LIPF technique is needed for concentration and temperature measurement. The accuracy of a two-line LIPF technique for H₂O concentration and temperature measurement is determined.     

Simple frequency measurement chain to 30 THz

We report harmonic mixing experiments between a 72 GHz mm-wave and 3.7 THz NH₃-laser radiation, as well as between 3.7 THz and the 10 m R(30) CO₂-laser line. For the former mixing a semiconductor diode is used, while for the higher frequencies an MIM tunnel diode served as the nonlinear element. Beat signals are of sufficient signal to noise ratio for precise optical frequency measurement.Visiting from National Institute of Metrology, Beijing, P. R. China