Quantitative CARS spectroscopy of the ν1 band of water vapour

The accuracy of CARS thermometry for H₂O vapour has been assessed under carefully controlled conditions for the temperature range 295 to 900 K and the pressure range 0.0066 to 2.7 atm. Excellent agreement between theory and experiment was achieved for line-broadening regimes ranging from Doppler broadening to motional narrowing. Various models for rotational energy transfer and line-broadening were compared and where pressure broadening dominated, excellent agreement was achieved with a simple linewidth model, dependent only on temperature and pressure. Excellent agreement was also achieved using either energy or angular momentum based relaxation models to model motionally narrowed spectra in the pressure range up to 2.7 atm. However, good agreement between theory and experiment depended on the inclusion of state mixing correction factors, and good thermometry accuracy at high temperature was sensitive to the value assumed for the water molecular polarisability.     

Doppler-free two-photon spectroscopy of the 2ν3 band of SF6

High-resolution spectroscopy of the 2ν₃ band of SF₆ is reported by means of Doppler-free two-photon transitions. Parts of spectra are measured with accuracy of 10⁻⁹. This technique applied to SF₆ should lead to an assignment of the spectra involved.     

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.     

CARS spectra of thermally excited SF6 molecules

CARS spectra of thev ₁ mode of thermally excited SF₆ were calculated numerically. The influence of the vibrational quasicontinuum on the CARS spectra has been considered by introducing different types of the homogeneous broadening at different vibrational levels. The appearance of additional lines in the CARS spectrum due to mixing of high-lying vibrational levels by Fermi coupling was considered numerically in the frame of a simple model. A comparison of calculated and experimental spectra has been made.     

Vibrational spectrum of uridine obtained by means of nonresonant-background-free CARS spectroscopy

Received: 18 June 1996/Revised version: 3 January 1997     

Self-focussing of CO2 laser radiation in SF6

Self-focussing of high-power TEA CO₂ laser pulses for a number of 10 m P-band lines is reported in SF₆ molecular gas. Application of this effect to estimating the intensity-dependent refractive index of the gas is demonstrated.     

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.     

H2 vibrational CARS thermometry

TheQ-branch spectra of molecular hydrogen have been used to determine rotational temperatures bycoherentanti-StokesRamanscattering (CARS). A supersonic jet expansion through a constant flow nozzle of adjustable temperature served as hydrogen source in the temperature range 300 to 2500 K. The analysis of the high-temperature data reveals details of the internal energy transfer in jet expansion.     

CARS in combustion: Prospects and problems

The principles of CARS are reviewed. This technique has achieved important successes in combustion, but its use has been limited mostly to temperature measurements. We demonstrate the feasibility of sensitive single-shot concentration measurements (to 0.2%) with fair accuracy, in spite of the adverse effects of turbulence and saturation. Even better sensitivities will be achieved using electronic resonance enhancement.     

Stimulated brillouin scattering in SF6 with a free-running XeCl laser as pump

A XeCl laser system without dispersive elements is used to investigate near threshold reflectivity and phase-conjugation (PC) fidelity of stimulated Brillouin scattering (SBS) mirrors with SF₆ as the active medium. Using different focal-length lenses to focus the broadband laser radiation into the Brillouin medium, it was found that at threshold the effective interaction length for SBS is equal to the confocal parameter and that the SBS gain is equal to its steady-state value for monochromatic pumping. High PC-fidelity values ranging from 0.8–1.0 were found under most of the experimental conditions investigated.     

Is rotational CARS an alternative to vibrational CARS for thermometry?

Recent developments in rotational CARS thermometry and critical issues when comparing vibrational and rotational CARS thermometry are described. In particular, the development of dual broadband rotational CARS and the noise characteristics of this approach are emphasized. The difficulty with unambiguous temperature determination in vibrational CARS with unknown parameters, in particular the nonresonant background susceptibility, and the lower sensitivity of rotational CARS thermometry at flame temperatures are also discussed.     

CARS studies of vibrationally excited nitrogen at low pressures

Coherent anti-Stokes Raman spectroscopy (CARS) was used to measure the vibrational temperature of microwave-excited nitrogen in a N₂–CO–He mixture. CARS spectra, originating from the N₂-vibrational levelsv=0 up tov=3, have been recorded by both narrowband scanning of the resonance region as well as by broadband OSA detection. For the microwave-excited N₂ molecules a vibrational temperatureT _v (N ₂ = (2130±110K) and a lower limit of detection forN ₂(v = 3) = 1.2 x 10¹⁵ cm^–3 was established. The CARS results were independently confirmed by simultaneously recorded and spectrally resolved CO infrared fluorescence studies.     

Aspects of hydrogen CARS thermometry

The temperature of hydrogen in a graphite tube furnace has been determined using broadband coherent anti-Stokes Raman scattering (CARS) spectroscopy. Significant laser-induced population changes were observed within the vibrational state manifold, whereas the rotational envelope in both fundamental and hot band remained unchanged.     

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.     

Broadband (1000 cm−1) multiplex CARS spectroscopy: Application to polarization sensitive and time-resolved measurements

A multiplex CARS spectrometer based on a cw diode-pumpedQ-switched Nd: YLF laser, a broadband dye-laser and a multichannel spectrum detection system has been constructed. Excellent mode characteristics of the laser beams and high pulse repetition rate (2 kHz) have resulted in good signal-to-noise ratio achieved with a few seconds accumulation time. A 1000 cm^–1 wide spectral range is covered in a single CARS spectrum with an expanded bandwidth of the dye laser. A thin-jet sampling method is used in order to avoid the phase-matching limitation. The efficient spectral intensity normalization by the reference (CCl₄) nonresonant spectrum and subsequent computer fitting have been implemented. The performance of the system is demonstrated by two different experiments. First, the polarization sensitive measurements (PS-CARS) of cyclohexane show its potential for accurate Raman depolarization ratio determination and for detection of weak (overlapped) Raman bands. Second, the transient resonance CARS measurement of the lowest excited triplet state of all-trans retinal indicate its feasibility to time-resolved CARS spectroscopy of fluorescent excited states.     

An evaluation of precision and systematic errors in vibrational CARS thermometry

The extraction of temperatures from experimental CARS spectra is discussed and demonstrated in an electrically heated over and a low-pressure flame. The present work is focused, in particular, on how the precision of CARS thermometry is limited by the accuracy with which the experimental parameters are known, on characteristics of the diode-array detector, on saturation effects due to stimulated Raman scattering and on the influence of spectral resolution on precision and accuracy.     

A study of CARS nitrogen thermometry at high pressure

The accuracy of CARS N₂ thermometry has been assessed using carefully measured experimental data at high pressures for the temperature range 295 to 870 K and pressure range 1–20 bar. Excellent agreement between calculated and experimental spectra was achieved using statistically based fitting laws to model rotational relaxation. Temperature errors of within ±60 K were achieved using the MEG fitting law, and within ±30 K using an extension to the model (XMEG). Results of separate ab initio IOS calculations with ECS corrections for rotational relaxation gave good overall agreement but did not model the structure of the motionally narrowed spectra as well as the empirical models. The various models were also compared with some complementary data measured by DLR, Stuttgart in their high pressure burner for pressures up to 40 bar. This study also investigated the sensitivity of CARS thermometry to pressure; in certain regions a significant reduction in sensitivity was found. Other key factors investigated include nonlinearities in the intensified diode array detector.Work supported by the CEC Project Turbulent Combustion and Diagnostics and by AEA Technology Underlying Programme     

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.     

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.     

CARS thermometry in a transversely heated graphite-tube atomizer used in atomic absorption spectrometry

An experimental setup for gas-temperature diagnostics using Coherent Anti-Stokes Raman Scattering (CARS) in very small sample volumes with great spatial and temporal temperature variations is presented. Studies have been started of a newly designed transversely heated graphite-tube atomizer for atomic absorption spectrometry (Perkin-Elmer, 4100 ZL). For the investigations, high spatial resolution and precise time synchronization of the measurements and also automatic control of the time-dependent intensity of the anti-Stokes signal were realized. The graphite-tube atomizer also offers the possibility of high-temperature-gas spectroscopy. A high-temperature CARS spectrum of CO₂, recorded in the graphite tube at 2300 K, is shown for the first time. A number of hot-band transitions in the spectral region of the Fermi doublet at a Raman shift from 1230 to 1450cm^–1 was observed and assigned, making possible the use of CO₂ as spectroscopic thermometer gas, similar to N₂.