Determination of temperature by stimulated raman scattering of molecular nitrogen,oxygen, and carbon dioxide

We have determined the temperature from SRS spectra of N₂-N₂, N₂-CO₂, O₂-O₂, and CO₂-CO₂ recorded in wide pressure and temperature ranges. The fitting procedure takes simultaneously into account the Dicke effect and motional narrowing. We have quantified the accuracy of the MEG and ECS-P models for rotational relaxation. The temperature extracted from each model is compared with thermocouple measurements. The influence of vibrational broadening and shifting is discussed in detail.     

Temperature and concentration measurements of molecular hydrogen in a filamentary discharge by coherent anti-stokes raman spectroscopy (CARS)

Coherent anti-Stokes Raman Spectroscopy (CARS) is applied to a filamentary discharge in H₂. Temperature and density profiles of molecular hydrogen are determined. The maximum temperature observed on the discharge axis is 5685 K. Vibrational and rotational transitions are analyzed and a difference in the evaluated temperatures is found which increases with pressure. In addition, the reactive thermal conductivity associated with dissociation is determined and compared with earlier work.     

Saturation spectroscopy of coherent raman scattering in molecular gases

We present the theory of two-photon Raman saturation of a two-level Raman transition studied by an independent CARS process. The main goal here is to probe the saturated homogeneous Raman line shape. It is shown that there appears a saturation dip with a width determined by the relaxation timeT ₁. In the case of Doppler-broadened line the coherent Raman saturation spectroscopy may be used to determine both theT ₁ andT ₂ relaxation times.     

Experimental study of vibrational and pure rotational coherent anti-stokes Raman scattering (CARS) in molecular hydrogen

Using a specially designed excimer-laser-pumped dye laser of adjustable bandwidth high-lying pure rotational transitions of both, ortho-and para-hydrogen have been identified by coherent anti-Stokes Raman scattering (CARS). As an interesting application H₂-based CARS-thermometry is discussed.     

High-resolution coherent stokes Raman spectroscopy of theν 1 andν 3 bands of methane

Coherent Stokes Raman spectra of the ν₁ and ν₃ bands of CH₄ have been recorded in mixing two pulsed lasers (ruby and dye) of very good spectral and spatial quality. The results show a resolution of about 0.010 cm⁻¹ for a 10 Torr pressure, corresponding in great part to Doppler broadening.     

Resonance enhanced coherent anti-stokes raman scattering and laser induced fluorescence applied to CH radicals: a comparative study

Resonance enhanced CARS and LIF have been applied to the CH radicals in a microwave excited Ar/H/CH plasma ( Pa, kW). Both techniques yield similar nonthermal rotational population distributions of CH(X) in its vibrational ground state (), which can be described by two rotational temperatures, K being in the order of the gas temperature for rotational states with , and a considerably higher for the higher rotational states. This result is in good agreement with previous resonance CARS and LIF measurements in similar plasmas. With resonance CARS additional measurements on CH in the state could be performed yielding a vibrational temperature of 2440 K, the total CH density was about m. The detection limits of both techniques are determined, in our case about CH radicals per quantum state in the detection volume, and their advantages and disadvantages are discussed. Received: 29 April 1996 / Accepted: 19 June 1996     

Collisional narrowing and spectral shift in coherent anti-stokes Raman spectra of molecular nitrogen up to 2500 bar and 700 K

CARS spectra of the N₂ Q-branch up to 2500 bar and 700 K have been measured. Calculated spectra based on theoretical models show significant disagreement with measured spectra above 300 bar so that CARS temperature measurements are in error by 130 K at 700 K and –150 K at 295 K. The spectral shift of the Q-branch reaches an asymptotic value corresponding to that measured in liquid nitrogen.     

Gas spectroscopy and temperature measurement by coherent Raman anti-stokes scattering

The feasibility of Raman spectroscopy and temperature measurements in gases by Coherent Anti-Stokes Scattering is discussed and demonstrated experimentally. Results are presented for H₂ gas at room temperature and also for H₂ liberated by pyrolysis in a Bunsen flame.     

Interferometric coherent Raman spectroscopy with incoherent light: Some applications

The theory of Interferometric Coherent Raman Scattering (ICRS) using twin broadband fields has recently been extended to include both resonant and nonresonant contributions to the signal. It is reviewed here. Valid for both ICARS and ICSRS, it is applied to new ICARS experiments on neat toluene and on alcoholic solutions of a methine dye. In each case the damped Rabi Detuning Oscillations (RDO), that are characteristic of ICRS, lead directly to vibrational frequencies and their dephasing times. The theory is also applied as a new way to determine the ratio of the nonresonant to resonant hyperpolarizabilities, accurately for toluene, and approximately for the methine dye solution whose (vibrationally) nonresonant contribution is negative.     

Stimulated raman scattering of fuel droplets

The strong stimulated Raman scattering (SRS) from diesel fuel droplets has the potential of providing the relative concentration of multicomponent fuel and the absolute size of individual droplets. The morphology-dependent resonances (MDRs) of a sphere cause the droplet to act as an optical resonator which greatly lowers the SRS threshold. The number density, quality factor, and frequency shift of several MDRs are calculated as a function of the ratio of the index of refraction of the liquid and the surrounding gas, which approaches unity at the thermodynamic critical condition for the fuel spray. The SRS spectra of monodispersed droplets of toluene, pentane, Exxon-Aromatic-150, and Mobil D-2 are presented. The exponential growth region of the SRS intensity I _1S as a function of the input laser intensity I _input is investigated for the toluene carbon ring breathing mode v ₂ and the pentane C-H stretching region. The I _1S ratio of toluene and pentane is measured as a function of the ratio of the toluene and pentane concentration for monodispersed droplets. The reduced fluctuation in I _1S when I _input is changed from multimode to single-mode is displayed as a histogram of the I _1S of the v ₂ mode of toluene droplets.     

Test of an optical parametric oscillator (OPO) as a compact and fast tunable stokes source in coherent anti-stokes raman spectroscopy (CARS)

An optical parametric oscillator (OPO), as a novel kind of broadband Stokes source, is employed for coherent anti-Stokes Raman spectroscopy (CARS). Compared to the conventional dye laser configuration OPO-CARS offers practical advantages. The tunable OPO allows a fast and comfortable frequency tuning. The excitation bandwidth of about 35 cm^–1 (FWHM) limits the spectral range of effective and stable single pulse CARS generation but can be used to enhance selected spectral structures.     

Coherent anti-Stokes Raman spectroscopy (CARS) of thev 3 band of methane in supersonic molecular beams

Supersonic molecular beams of methane are investigated in the expansion region using coherent anti-Stokes Raman scattering (CARS). Raman spectra of thev ₃ vibration with resolved rotational structure at low temperatures are reported. Comparison with calculated CARS spectra shows that the rotational distribution in the beam may be well described by a Boltzmann distribution. Temperatures are the same for all three nuclear spin modifications within the experimental error.     

The application of single-pulse CARS for temperature measurements in a turbulent stagnation flame

N₂ Q-branch CARS spectra have been recorded and evaluated for temperature determination in a turbulent, premixed CH₄/air stagnation flame with a burner of 40 mm diameter and 22 kW thermal load. Temperature histograms on the flame axis at different distances from the stagnation plate have been measured. Problems of practical applicability are addressed, including those arising from the limited spatial resolution of the BOXCARS geometry, from an insufficient dynamic range of the diode array detector, and from a memory effect of the detector in the case of measurements in highly turbulent flame areas with strong intermittency. Some information is given on the computerized acquisition and on the evaluation of the large amounts of data that are necessary for extensive investigations in large combustion systems.     

Rotational temperature behaviour in supersonic jet expansions of molecular nitrogen

The rotational temperature behaviour in adiabatic jet expansion of molecular nitrogen is investigated over a wide range of stagnation density and nozzle diameter values using coherent anti-Stokes Raman spectroscopy (CARS). Estimates of rotational collisional numbers are made for both (N₂+N₂) and (N₂+Ar) systems. The aspect of cluster formation for both systems is also discussed.     

Infrared degenerate four-wave mixing and resonance-enhanced stimulated Raman scattering in molecular gases and free jets

2 H₂), methane (CH₄), carbon dioxide (CO₂), and nitrous oxide (N₂O) in a cell under equilibrium conditions and cooled in free jet expansions. For methane at room temperature the detection limit was 2×10¹² molecules per cm³ and quantum state, enabling the detection of trace species with a spatial resolution of 1 mm²×30 mm. In an attempt to study transitions in the ν₁+ν₃ and 2ν₂+ν₃ combination bands of CO₂ or N₂O, it was not possible to observe any DFWM signal. Instead a surprisingly strong, backward- and forward-directed emission was found which could not be attributed to the DFWM process. The signal arising from this emission was more than 2 orders of magnitude stronger than the DFWM signals obtained for other molecules. The frequencies of the emitted radiation were found to correlate with the transitions ν₁+ν₃→ν₁ and 2ν₂+ν₃→2ν₂, respectively. Our investigations lead to the conclusion that the emission can be explained by stimulated Raman scattering, resonantly enhanced by transitions to the combination levels ν₁+ν₃ and 2ν₂+ν₃. This process seems to suppress the generation of DFWM signals. Received: 1 October 1996/Revised version: 6 January 1997     

Structural changes in excited states and photoisomers determined by time-resolved Raman scattering

Molecules in the excited singlet and triplet state and photoproducts occuring after photoisomerization or proton transfer are investigated by time-resolved resonance Raman and resonance CARS spectroscopy with nanosecond time resolution. From the time-resolved spectra information on structures and bond strengths of these short-lived species and on their kinetics are obtained.     

H2 CARS thermometry in a fuel-rich,premixed, laminar CH4/air flame in the pressure range between 5 and 40 bar

To establish H₂ CARS thermometry at high pressure, accumulated H₂ Q-branch CARS spectra were recorded in the exhaust of a fuel-rich CH₄/air flame at pressures between 5 and 40 bar. Temperatures were deduced by fitting theoretical spectra to experimental data points. The Energy-Corrected Sudden (ECS) scaling law was employed to set up an empirical model for the calculation of H₂ linewidths in high-pressure hydrocarbon flames with H₂ as a minority species. Experimental H₂ CARS spectra could be simulated very accurately with this model. The evaluated temperatures agreed well with reference temperatures obtained by spontaneous rotational Raman scattering of N₂.     

Oxygen concentration and temperature measurements in N2–O2 mixtures using rotational coherent anti-Stokes Raman spectroscopy

The accuracy and precision of oxygen concentration and temperature measured by dual-broadband rotational Coherent Anti-Stokes Raman Spectroscopy (CARS) were investigated in nitrogen-oxygen mixtures at atmospheric pressure and temperatures between 290 and 1410 K. The relative standard deviation of temperatures evaluated from pure oxygen rotational CARS spectra was found to be around 5%, and the mean temperature was the same as for nitrogen CARS spectra, except for temperatures above 1000 K, where the temperature was 120 K below the correct value. The in situ calibrated oxygen concentrations were within 10% of the correct value, with a standard deviation of around 1.2% for the mixtures of 12 and 20% oxygen in nitrogen. For the lowest oxygen concentrations considered in this study (2 and 4%), the systematic errors in the evaluated concentrations were very large, and the standard deviation of repeated single-shot measurements was above 2%. However, employing weighting in the spectral fitting routine reduced the errors in the concentration and the single-shot standard deviation was lowered to 0.5%. Finally, it was shown that spectral interference (from oxygen) in a rotational CARS spectrum of nitrogen generally had little impact on the temperature evaluated from fitting the spectra to theoretical nitrogen spectra.     

Coherent raman spectroscopy of nitrogen molecules and clusters in supersonic jets

Coherent Stokes and anti-Stokes Raman scattering CSRS and CARS have been employed to study the spectroscopy of nitrogen molecules and clusters in the expansion of a supersonic jet. In the vibrational spectrum, at strong stagnation conditions, an intense redshifted peak is observed which can be assigned to the intramolecular vibrations in large N₂ clusters having adopted the -phase structure. Another weak feature is assigned to nitrogen clusters in the -phase. In the rotational region of the spectrum only monomer features have been observed. The failing to observe librational motions is consistent with the finding that the nitrogen clusters are predominantly in the orientationally unordered -phase. The low rotational temperature suggests supercooling of the -phase.