Single diode laser sensor for wide-range H2O temperature measurements

A single diode laser absorption sensor (near 1477 nm) useful for simultaneous temperature and H2O concentration measurements is developed. The diode laser tunes approximately 1.2 cm(-1) over three H2O absorption transitions in each measurement. The line strengths of the transitions are measured over a temperature range from 468 to 977 K, based on high-resolution absorption measurements in a heated static cell. The results indicate that the selected transitions are suitable for sensitive temperature measurements in atmospheric pressure combustion systems using absorption line ratios. Comparing the results with HITRAN 96 data, it appears that these transitions will be sensitive over a wide range of temperatures (450-2000 K), suggesting applicability for combustion measurements.     

Absorption line shift with temperature and pressure: impact on laser-diode-based H2O sensing at 1.393 microm

High-resolution absorption measurements of the H2O line in the v1 + v3 band at 1.3928 microm were made in the temperature range of 296-1100 K by use of an InGaAsP distributed-feedback laser diode operating at 1.39 microm. Spectral line shift, line strength, and N2 broadening on the water-vapor line and their impact on the accuracy of optical-absorption-based gas sensing have been investigated. The results obtained were compared with values obtained from the HITRAN database and values reported in the literature, facilitating H2O sensing in a nonstandard temperature and pressure environment.     

Diode-Laser Absorption Measurements of CO(2) Near 2.0 mum at Elevated Temperatures

A diode-laser sensor system based on absorption spectroscopy techniques has been developed for nonintrusive measurements of CO(2) in high-temperature environments. Survey spectra of the CO(2) (20 degrees 1,04 degrees 1)(I)-00 degrees 0 and (20 degrees 1,04 degrees 1)(II)-00 degrees 0 bands between 1.966 and 2.035 mum (4915-5085 cm(-1)) were recorded at temperatures between 296 and 1425 K in a heated static cell and compared with calculated spectra (by using the HITRAN 96/HITEMP database) to find candidate transitions for CO(2) detection. High-resolution measurements of the CO(2) R(56) line shape [(20 degrees 1,04 degrees 1)(II)-00 degrees 0 band] were used to determine the transition line strength, the self-broadening half-width, and the coefficient of temperature dependence of the self-broadening half-width. The results represent what are believed to be the first measurements of CO(2) absorption near 2.0 mum with room-temperature diode lasers. Potential applications of the diode-laser sensor system include in situ combustion measurements and environmental monitoring.     

Intracavity absorption spectroscopy with a tunable multimode traveling-wave ring Ti:sapphire laser

A tunable multimode unidirectional traveling-wave Ti:sapphire laser was developed to measure in situ the atmospheric absorption spectra using intracavity absorption spectroscopy. The effective absorption path length was 2100 km. O2 and H2O vapor lines in atmosphere with absorption coefficients of 10(-6)-10(-8) cm(-1) were measured with uncertainties <5%, and the absorption coefficients were in agreement with those estimated from the HITRAN database. By tuning the wavelength, a weak absorption line with an absorption coefficient of 10(-9) cm(-1) was measured with a sensitivity of 2×10(-10) cm(-1). The sensitivity was limited by the residual parasitic variation that appeared in the spectrum.     

Temperature measurements in a rapid compression machine using mid-infrared H₂O absorption spectroscopy near 7.6 μm

A method for measuring the temporal temperature and number density in a rapid compression machine (RCM) using quantum cascade laser absorption spectroscopy near 7.6?μm is developed and presented in this paper. The ratios of H₂O absorption peaks at 1316.55 cm^-1 and 1316.97 cm^-1 are used for these measurements. In order to isolate the effects of chemical reactions, an inert mixture of argon with 2.87% water vapor is used for the present investigation. The end of compression pressures and temperatures in the RCM measurements are P_C=10, 15, and 20 bar in the range of T_C=1000 to 1200?K. The measured temperature history is compared with that calculated based on the adiabatic core assumption and is found to be within ±5 K. The measured temporal number density of H₂O to an accuracy of 1%, using the absolute absorption of the two rovibrational lines, show that the mixture is highly uniform in temperature. A six-pass, 5.08?cm Herriott cell is used to calibrate the line strengths in air and broadening in an Ar bath gas.     

Tunable diode-laser absorption measurements of NO(2) near 670 and 395 nm

Two single-mode diode lasers were used to record high-resolution absorption spectra of NO(2) (dilute in Ar) near 670.2 and 394.5 nm over a range of temperatures (296 to 774 K) and total pressures (2.4 × 10(-2) to 1 atm). A commercial InGaAsP laser was tuned 1.3 cm(-1) at a repetition rate of 1 kHz to record the absorption spectra near 670.2 nm. In separate experiments with a prototype system, an external-cavity GaAlAs laser was frequency doubled with a quasi-phase-matched LiNbO(3) waveguide and tuned 3.5 cm(-1) to record absorption spectra near 394.5 nm. Variations of the spectral absorption coefficients with temperature and pressure were determined from measured spectra.     

Photoacoustic distributed feedback laser spectroscopy on hydrogen fluoride

We have developed a photoacoustic spectrometer based on a distributed feedback (DFB) diode laser. The single-mode emission of the laser can be tuned continuously over 700 GHz enabling the precise determination of absorption line parameters. Our experiments were performed on the rotational lines P2 and P3 of the vibrational transition 2-0 (overtone) of hydrogen fluoride (HF) at 1304.534 nm and 1312.591 nm (vacuum), respectively. The pressure broadening coefficient due to elastic collisions with N(2) molecules is found to be 5.92 +/- 0.04 GHz/atm (296 K) and 5.38 +/- 0.04 GHz/atm, respectively. The Doppler linewidths turn out to be 630 +/- 40 MHz and 670 +/- 40 MHz (296 K), respectively. The pressure-induced line shifts of the absorption lines for N(2) are 540 +/- 40 MHz/ atm and 580 +/- 40 MHz/atm, respectively.     

Large-modulation-depth 2f spectroscopy with diode lasers for rapid temperature and species measurements in gases with blended and broadened spectra

A method that uses tunable diode lasers is developed for rapid temperature and concentration measurements of gases with highly broadened and congested spectra. Wavelength modulation absorption spectroscopy with 2f detection is utilized, because this derivative method offers benefits in dealing with blended spectral features. The 2f signal depends critically on the modulation depth of the laser alpha, which is increased to values above those typically achieved when wavelength modulation spectroscopy with diode lasers is performed. The 2f method with large modulation depths is validated by using near-IR diode lasers to probe pressure-broadened water-vapor features in the 1.4-microm region over a range of temperatures from 296 to 800 K and at pressures as high as 20 atm. Modulation depths as high as alpha = 0.8 cm(-1) are attained at modulation frequencies of 50 kHz and measurement bandwidths of 15 kHz. Comparisons of experimental results with 2f simulations, based on the HITRAN spectral database, provide confirmation of the capability of this method for rapid measurements of gas temperature and species concentration.     

Diode laser sensor for measurements of CO, CO(2), and CH(4) in combustion flows

A diode laser sensor has been applied to monitor CO, CO(2), and CH(4) in combustion gases with absorption spectroscopy and fast extraction-sampling techniques. Survey spectra of the CO 3nu band (R branch) and the 2nu(1) + 2nu(2)(0) + nu(3) CO(2) band (R branch) near 6350 cm(-1) and H(2)O lines from the nu(1) + 2nu(2) and 2nu(2) + nu(3) bands in the spectral region from 6345 to 6660 cm(-1) were recorded and compared with calculated spectra (from the HITRAN 96 database) to select optimum transitions for species detection. Species concentrations above a laminar, premixed, methane-air flame were determined from measured absorption in a fast-flow multipass absorption cell containing probe-sampled combustion gases; good agreement was found with calculated chemical equilibrium values.     

Water vapour foreign-continuum absorption in near-infrared windows from laboratory measurements

For a long time, it has been believed that atmospheric absorption of radiation within wavelength regions of relatively high infrared transmittance (so-called 'windows') was dominated by the water vapour self-continuum, that is, spectrally smooth absorption caused by H(2)O--H(2)O pair interaction. Absorption due to the foreign continuum (i.e. caused mostly by H(2)O--N(2) bimolecular absorption in the Earth's atmosphere) was considered to be negligible in the windows. We report new retrievals of the water vapour foreign continuum from high-resolution laboratory measurements at temperatures between 350 and 430?K in four near-infrared windows between 1.1 and 5?μm (9000-2000?cm(-1)). Our results indicate that the foreign continuum in these windows has a very weak temperature dependence and is typically between one and two orders of magnitude stronger than that given in representations of the continuum currently used in many climate and weather prediction models. This indicates that absorption owing to the foreign continuum may be comparable to the self-continuum under atmospheric conditions in the investigated windows. The calculated global-average clear-sky atmospheric absorption of solar radiation is increased by approximately 0.46?W?m(-2) (or 0.6% of the total clear-sky absorption) by using these new measurements when compared with calculations applying the widely used MTCKD (Mlawer-Tobin-Clough-Kneizys-Davies) foreign-continuum model.     

Detection of high-temperature water vapor at 940 nm with vertical-cavity surface-emitting lasers

A vertical-cavity surface-emitting laser was used to study the absorption of water vapor in the 940 nm region. Measurements for several absorption lines within the 2 v1 + V3 vibrational band were performed. Line strengths at room temperature and in a heated absorption cell over the temperature range of 420-970 K were obtained. The line strength values were in good agreement with simulations based on the values of the HITRAN 2004 database. The measurements also showed that water vapor transitions near 940 nm are suitable for sensitive temperature determination.     

H(2)O--N(2) collision-induced absorption band intensity in the region of the N(2) fundamental: ab initio investigation of its temperature dependence and comparison with laboratory data

The present paper aims at ab initio and laboratory evaluation of the N(2) collision-induced absorption band intensity arising from interactions between N(2) and H(2)O molecules at wavelengths of around 4?μm. Quantum chemical calculations were performed in the space of five intermolecular coordinates and varying N--N bond length using M?ller-Plesset perturbation and CCSD(T) methods with extrapolation of the electronic energy to the complete basis set. This made it possible to construct the intermolecular potential energy surface and to define the surface of the N--N dipole derivative with respect to internal coordinate. The intensity of the nitrogen fundamental was then calculated as a function of temperature using classical integration. Experimental spectra were recorded with a BOMEM DA3-002 FTIR spectrometer and 2?m base-length multipass White cell. Measurements were conducted at temperatures of 326, 339, 352 and 363?K. The retrieved water-nitrogen continuum significantly deviates from the MT_CKD model because the relatively strong nitrogen absorption induced by H(2)O was not included in this model. Substantial uncertainties in the measurements of the H(2)O-N(2) continuum meant that quantification of any temperature dependence was not possible. The comparison of the integrated N(2) fundamental band intensity with our theoretical estimates shows reasonably good agreement. Theory indicates that the intensity as a function of temperature has a minimum at approximately 500?K.     

Infrared collision-induced absorption by N(2) near 4.3 μm for atmospheric applications: measurements and empirical modeling

Accurate measurements of collision-induced absorption by pure nitrogen in the fundamental band near 4.3 μm have been made in the 0-10 atm and 230-300 K pressure and temperature ranges, respectively. A Fourier-transform spectrometer was used with a resolution of 0.5 cm(-1). The current measurements, which agree well with previous ones but are more precise, reveal that weak features are superimposed on the broad N(2) continuum. These features have negligible temperature dependence, and their origin is not clear at the present time. Available experimental data in the 190-300 K temperature range have been used to build a simple empirical model that is suitable for use to compute atmospheric N(2) absorption. Tests indicate that this model is accurate unlike the estimates produced by widely used atmospheric transmission codes.     

Modeling of gas absorption cross sections by use of principal-component-analysis model parameters

Monitoring the amount of gaseous species in the atmosphere and exhaust gases by remote infrared spectroscopic methods calls for the use of a compilation of spectral data, which can be used to match spectra measured in a practical application. Model spectra are based on time-consuming line-by-line calculations of absorption cross sections in databases by use of temperature as input combined with path length and partial and total pressure. It is demonstrated that principal component analysis (PCA) can be used to compress the spectrum of absorption cross sections, which depend strongly on temperature, into a reduced representation of score values and loading vectors. The temperature range from 300 to 1000 K is studied. This range is divided into two subranges (300-650 K and 650-1000K), and separate PCA models are constructed for each. The relationship between the scores and the temperature values is highly nonlinear. It is shown, however, that because the score-temperature relationships are smooth and continuous, they can be modeled by polynomials of varying degrees. The accuracy of the data compression method is validated with line-by-line-calculated absorption data of carbon monoxide and water vapor. Relative deviations between the absorption cross sections reconstructed from the PCA model parameters and the line-by-line-calculated values are found to be smaller than 0.15% for cross sections exceeding 1.27 x 10(-21) cm(-1) atm(-1) (CO) and 0.20% for cross sections exceeding 4.03 x 10(-21) cm(-1) atm(-1) (H2O). The computing time is reduced by a factor of 10(4).     

Accurate frequency measurements for H(2)O and (16)O(3) in the 119-cm(-1)OH atmospheric window

We report frequency measurements for relatively weak H(2)O and (16)O(3) rotational transitions in the ground state and in the nu(2) = 1 vibrationally excited state. We obtained the frequency measurements by using the laboratory technique of tunable far-infrared spectroscopy with the objective of improving H(2)O and O(3) line parameters required for modeling the important atmospheric spectral window near 119 cm(-1). New sets of molecular constants are calculated from the (16)O(3) data, and improved values are reported for the frequencies of the H(2)O lines. The improvement in atmospheric simulations obtained with the new results is illustrated by comparison with recent high-resolution balloon-based atmospheric measurements. These new data significantly improve simulations of high-resolution atmospheric emission spectra.     

Isotope (18)O/(16)O Ratio Measurements of Water Vapor by use of Photoacoustic Spectroscopy

We applied a photoacoustic spectroscopy technique to isotope ratio measurements of (16)O and (18)O in water-vapor samples, using a pulsed tunable dye laser pumped by a Nd:YAG laser. The fourth overtone bands (4nu(OH)) of water molecules near 720 nm were investigated. We identified the absorption lines of H(2)(16)O and H(2)(18)O in the photoacoustic spectra that we measured by using an (18)O-enriched water sample and the HITRAN database. We measured the difference in the (18)O/(16)O isotope ratios for normal distilled water and Antarctic ice, using the photoacoustic method. The value obtained for the difference between the two samples is delta(18)O = -32 ? 16 per thousand, where the indicated deviation was a 1varsigma value among 240-s measurements, whereas the value measured with a conventional isotope mass spectrometer was delta(18)O = -28 ? 2 per thousand. This method is demonstrated to have the potential of a transportable system for in situ and quick measurements of the H(2)(18)O/H(2)(16)O ratio in the environment.     

Extensive measurements of H216O line frequencies and strengths: 5750 to 7965 cm(-1)

High-resolution spectra of H(2)(16)O vapor covering the region from 5750 to 7965 cm(-1) were used to determine experimental values of line positions and strengths of over 3750 vibration-rotation transitions in the (110)-(000), (011)-(000), (040)-(000), (120)-(000), (021)-(000), (200)-(000), (101)-(000), (002)-(000), (031)-(010), (210)-(010) and (111)-(010) bands from which rotational energy levels in the (040), (120), (021), (200), (101) and (002) vibrational states were obtained. The line strengths and frequencies reported here are considered to be a marked improvement over the values listed in the 1986 edition of the HITRAN database, and a preliminarly listing from this work has been included in the 1993 HITRAN edition.     

Application of a diode-laser absorption technique with the d(2) transition of atomic rb for hypersonic flow-field measurements

With a first application of semiconductor lasers to absorption measurements of seeded atomic Rb in high-enthalpy flow fields, a diagnostic technique for time-resolved determination of flow velocity and gas temperature with a line-shape analysis was developed. In our measurements a GaAlAs diode laser was used to scan repetitively at 15 kHz over 1.3 cm(-1) across the D(2) resonance transition (5S(1/2) ? 5P(3/2), 780.2 nm) of seeded atomic Rb to obtain multiple absorption line shapes. The time-dependent signal contains highly resolved spectral line-shape information, which we interpret by fitting the spectrally resolved line shapes to Voigt profiles. Kinetic temperatures in the range 900-1400 K and gas velocities in the range 3900-6200 ms(-1) were obtained from the Doppler-broadened component of the line shape and from the Doppler shift, respectively, of the absorption frequency.     

Update of line parameters of ozone in the 2550-2900 cm(-1) region

An update of spectroscopic line parameters for the 3.45-3.92 microm ozone bands is reported. The line list includes the parameters of 15 bands of the main isotopic species and of the v1+v2+v3 band of 16O16O18O and 16O18O16O. The results are based on previous high resolution laboratory studies. Comparisons of experimental spectra with an absorptance simulation of ozone based on the reported line list shows that the latter one is accurate enough for strong, medium, and weak transmittance in the 2550-2900 cm(-1) spectral range. The data are available on the Web in the Spectroscopy and Molecular Properties of Ozone (S&MPO, http://smpo.iao.ru and http://ozone.univ-reims.fr) and HITRAN (http://cfa-www.harvard.edu/hitran/) databanks.     

Development of a Tunable, Narrow-Linewidth, CW 2.066-mum Ho:YLF Laser for Remote Sensing of Atmospheric CO(2) and H(2)O

A smoothly tunable, narrow-linewidth, cw, 32-mW, 2.066-mum Ho:YLF laser was constructed and used for the first time in preliminary spectroscopic measurements of atmospheric CO(2) and H(2)O. The laser was constructed with a 4.5-mm-long, TE-cooled, codoped 5% Tm and 0.5% Ho yttrium lithium fluoride crystal (cut at Brewster's angle) pumped by an Ar(+)-pumped 500-mW Ti:sapphire laser operating at 792 nm. Intracavity etalons were used to reduce the laser linewidth to approximately 0.025 cm(-1) (0.75 GHz), and the laser wavelength was continuously and smoothly tunable over approximately 6 cm(-1) (180 GHz). The Ho:YLF laser was used to perform spectroscopic measurements on molecular CO(2) in a laboratory absorption cell and to measure the concentration of CO(2) and water vapor in the atmosphere with an initial accuracy of approximately 5-10%. The measurement uncertainty was found to be due to several noise sources, including the effect of asymmetric intensity of the laser modes within the laser linewidth, fluctuations caused by atmospheric turbulence and laser beam/target movement, and background spectral shifts.