Detection of ozone by differential absorption using CO2 laser

The differential absorption method with the conventional CO₂ laser is discussed for the detection and monitoring of ozone in ambient atmosphere. By using the P(14) line in the (00°1 to 02°0) and the R(16) line in the (00°1 to 10°0) band, the measurement of ozone was made in a field. As an experimental result, the minimum detectable concentration of 0.15 ppm was obtained with the system, and the concentration of 0.2 ppm was measured in a photo-chemical smog.     

Quantitative high temperature absorption spectroscopy of NCO at 305 and 440 nm

A spectral survey of NCO absorption near the P₂ + ^pQ₁₂ head of the [A²Σ + (00⁰0)←X²Π_i(00¹0)] band was obtained at 1450°K, 0.6 atm using a remotely located cw ring dye laser source and a shock tube. Mixtures of hydrogen cyanide, oxygen and nitrous oxide diluted in argon were shock heated to provide a reproducible steady-state concentration of NCO, and narrow-line absorption was measured in repeated experiments with the laser set at different wavelengths. The peak absorption was found at 440.479 nm (vac). The experimental spectrum was compared with a theoretical model to yield an average Voigt parameter a ? 0.1. Additional experiments, in mixtures of cyanogen, oxygen and nitrous oxide diluted in argon, provided a known plateau level of NCO, which was used to infer an absolute absorption coefficient β(1450°K, 0.60 atm) = 110(-50, +130) cm^-1 atm^-1 at 440.479 nm. This value of β corresponds to an oscillator strength of 0.0026 for the (00⁰0←00¹0) band.Similar experiments were conducted to monitor the absorption around the R₁ head of the [B²Π_i(10¹0)←X²Π_i(00¹0)] band of NCO, using a frequency doubled cw ring dye laser. The observed spectrum displayed strong broadening, indicating predissociation of the upper state. At the peak absorption wavelength (304.681 nm, vac), we inferred β(1470°K, 0.63 atm) = 40(-19, +48) cm^-1 atm^-1 and a ? 9. This value of β corresponds to an oscillator strength of 0.0031 for the (10¹0←00¹0) band.     

Radio frequency excited waveguide CO2 lasers on sequence-band transitions

2 lasers based on either a quartz or an alumina waveguide were studied on the 00°2 - [10°1,02°1]_I,II sequence bands. A compact multisegment RF excitation with capacitive coupling was used for pumping the gain section of the laser waveguide. The use of a separate intracavity hot CO₂ waveguide suppresses the regular-band transitions. The quartz waveguide laser has a total of 62 lines lasing on both the 9.4 and 10.4 μm sequence bands. The alumina waveguide laser has 40 lines lasing on the 10.4 μm sequence band. These lasers can be either pulsed or continuous-wave (CW) operated on the selected line without a line jumping problem. Received: 29 September 1997/Revised version: 2 December 1997     

Heterodyne frequency measurements on N2O between 1257 and 1340 cm−1

Frequency measurements are given for the 00⁰1-00⁰0 and 01¹1-01¹0 bands of N₂O from 1257 to 1340 cm^?1. The measurements utilize heterodyne techniques by measuring small frequency differences between a tunable diode laser locked to the center of an N₂O absorption line and harmonic combinations of frequencies of radiation from two CO₂ Lamb-dip-stabilized lasers. The measurements are facilitated by the use of the CO laser as a transfer laser whose frequency is also measured. These measurements have been combined with other data to provide new band constants and frequency calibration tables for several band systems of N₂O in the following regions; 1215 to 1340, 1816 to 1930, and 2135 to 2268 cm^?1. A correction factor is also provided for existing calibration tables near 590 cm^?1.     

R-branch head of the ν3 band of CO2 at elevated temperatures

The R-branch head of the 00⁰1 ← 00⁰0 band of ¹²C¹⁶O₂ has been recorded with Doppler-limited resolution using a tunable laser difference-frequency spectrometer. J values to 140 were measured at temperatures to 985 K. The data have been combined with extremely precise transition frequencies for 0 ≤ J ≤ 76 measured with a Fourier transform interferometer to obtain an improved set of spectral constants for this ν₃ band of CO₂.     

On the transition moment of the CO2 40°1II-00°0 band near 7740 cm-1

Using intensity measurements on the CO₂ 40°1_II-00°0 band obtained by Valero and Boese, we have expanded the F(m)-factor for the parallel band by using the Herman-Wallis formula. We have calculated the transition moment and determined the coefficients in the expansion of F(m).     

Absolute frequency measurements of the 0002-0000, 2001-0000, and 1201-0000 bands of N2O by heterodyne spectroscopy

The absolute frequencies of 39 lines in the 00⁰2-00⁰0, 20⁰1-00⁰0, and 12⁰1-00⁰0 bands of N₂O in the range 4300–4800 cm^?1 have been measured by heterodyne frequency techniques. The lines were each measured in Doppler-limited absorption, with a color-center laser as a tunable probe of the N₂O and two stabilized CO₂ lasers as reference frequencies. New rovibrational constants have been fitted to these measurements. Tables of calculated transition frequencies are given, with estimated absolute uncertainties as small as 10^?4 cm^?1. The pressure shifts of four lines have been measured, and the values fall within the range of 0 to ?2 MHz/kPa (0 to ?0.2 MHz/Torr).     

New N2O laser band in the 10 μm wavelength region

Fifty new laser lines have been observed in continuous emission from an N₂O laser by placing a hot N₂O absorber cell inside the laser cavity to suppress the regular laser lines. The new lines are identified as rotation-vibration transitions of the (00⁰2–10⁰1) band of N₂O.     

Measurement of line intensities of linear molecules under low resolution

By using the relation k_v?S_J/δ_J applicable at sufficiently high pressures, at which the rotational fine structure in a band is smeared out completely, line intensities S_J may be determined from measured spectral absorption coefficients and known local line spacings δ_J. First, the validity of the approximation is ascertained by comparing the spectral absorption coefficient data of Penner and Weber and of Varanasi and Penner for the fundamental bands of CO and NO, respectively, with S_J/δ_J derived from the high resolution measurements of Benedict et al. (for CO) and of Abels and Shaw (for NO). Line intensity data obtained using this method are in good agreement with the high-resolution measurements of Toth (grating spectroscopy) for some unblended lines in the 00°0?02°1 band of N₂O and of Lacome et al. (laser- spectroscopy) for lines in the 10°0?00°1 band of N₂O.     

Fine frequency tuning of high power TEA CO2 lasers

A new technique is proposed to fine tune a TEA CO₂ laser within the bandwidth of a single ro-vibrational emission line. A tuning range of ±2 GHz off line center is obtained with an emission bandwidth of about 250 MHz and with a total energy output exceeding 1 joule at line center for the P20 (00°1–10°0) line. This technique can be used for single longitudinal mode operation and has the advantage of being directly scalable to higher power lasers.     

Measurement at different temperatures of absolute intensities,line half-widths,and broadening by Ar and N2 for the 3001II←0000 band of CO2

Absolute intensities, self-broadening coefficients, and foreign-gas broadening by Ar and N₂ were measured at temperatures of 197, 233 and 294 K for the 30⁰1_II←00⁰0 band of CO₂ at 6348 cm^-1. Also, the intensity parameters and total band intensity were calculated. We obtained for the vibration-rotation interaction factor the value F(m) = 1 + (0.26 ± 0.06) × 10^-2m + (0.92 ±0.32 × 10^-4 m²; for the purely vibrational transition moment, we found ¦R₀₀₀₀^3001_II¦к(0.4351 ± 0.0014)()10^b3 debye; and, for the total band intensity at STP conditions, S_band(30⁰1_II←00⁰0)_STP = 1255 ± 9 cm^-1 km^-1 atm^-1.Self-broadening coefficients at 197 and 294 K were also measured, as well as broadening by Ar and N₂. Foreign-gas-broadening efficiencies (Ar and N₂) were determined. Finally, a comparison is made with measurements by other authors and with theoretically calculated values.     

Line intensities of CO2 in the 2·7 micron region

Individual line intensities have been measured at 0·025 cm^?1 resolution and low pressures for the two strong Σ-Σ bands of C¹²O₂¹⁶ near 2.7 microns, as well as for their associated Π-Π hot-bands. Values of the rotationless dipole-moment matrix elements and vibration-rotation interaction coefficients are reported along with total band intensities. Results for the latter in cm^?2 atm^?1 at 296°K are: 25·7, 1·96, 39·3 and 3·23 for the 02⁰1-00⁰0, 03¹1-01¹0, 10⁰1-00⁰0, and 11¹1-01¹0 bands, respectively.     

Shock-tube study of HCN self-broadening and broadening by argon for the P(10) line of the ν1 band at 3 μm

A tunable infrared diode laser was used to measure the fully resolved absorption line shape of the P(10) line in the ν₁ band (10°0–00°0) of HCN for shock-heated mixtures of HCN-Ar at temperatures of 1000, 1500 and 2000 K. The temperature dependence of the collision-broadening coefficients 2γ (cm^-1 atm^-1, FWHM) were inferred for both self-broadening and broadening by argon. For the assumed form 2γ = 2γ₀(T₀/T)ⁿ the exponent n was determined to be 0.63 ± 0.06 with 2γ₀ = 0.11 cm^-1atm^-1 and T₀ = 300 K for argon-broadening in the range 300 < T < 2000 K, and 1.2 ± 0.6 with 2γ₀ = 0.68 cm^-1atm^-1 and T₀ = 1000 K for self-broadening in the range 1000 < T < 2000 K.     

Line strengths and self-broadened linewidths of N2O in the 2-μm region: 2400-0000 and 0112-0000 transitions

The strenghths and self-broadened linewidths of the parallel 24⁰0-00⁰0 and perpendicular 01¹2-00⁰0 bands of N₂O have been measured with a precision better than 3%, using a deconvolution procedure. For both transitions, the coefficient of the vibration-rotation interaction polynomial, the values of the rotationless dipolar transition moment, and the band intensity have been calculated from the line strengths. For the total intensity the values found are S_00⁰0²⁴⁰⁰ = (1.325 ± 0.021) × 10^?2 cm^?2·atm^?1 and S_00⁰0⁰¹¹² = (1.209 ± 0.018) × 10^?2 cm^?2·atm^?1.     

Sequence and Hot Transitions in the Co2 Molecule; Interference of Adjacent Lines Belonging to Different Transitions as a Function of Temperature

Carbon-dioxide spectra of some higher transitions in the 9-11μm region were studied. Spectra of the sequence ([10°1,02°1]_I,II - 00°2) and hot (01¹1 - 11¹0) bands were calculated as a function of temperature. the positions of the ro-vibrational transitions and their intensities were determined as a function of temperature. for lines in hot and sequence transitions whose positions are close to some of the regular lines ([l0⁰0,02⁰0]_I,II - 00°1)¹ absorption coefficients of adjacent lines were calculated as functions of line center distances and temperature. the resulting values of the absorption coefficient for conditions of constant pressure or constant volume were determined.     

Largeurs des raies de la transition 00°1 → (10°0; 02°0)I de CO2 perturbe par l'argon

Argon-pressure broadened CO₂ linewidths have been measured in the 00°1- (10°0,02°0)_I bands using a stabilized laser source. It is shown that a short-range anisotropic potential must be introduced in the calculation of the interruption function, in order to avoid the use of adjustment procedures of questionable physical meaning. An order of magnitude for the parameters of this potential is estimated empirically. The importance of non additivity effects in the interaction potential for the calculation of the interuption function is pointed out. When a treatment, which takes into account deviations from straight trajectories for strong collisions is adopted, the theoretical results compare well with experimental data.     

High-resolution infrared spectrum of the 859- and 1711-cm−1 bands of carbonyl sulfide (OCS)

The ν₁ and 2ν₁ bands of OCS have been measured using grating spectrometers and a tunable diode laser spectrometer. Preliminary wavenumbers for OCS absorption lines useful for calibrating tunable laser systems are given for the wavenumber intervals 825 to 885 cm^?1 and 1665 to 1737 cm^?1. Measurements and an analysis are given for the bands 10⁰0-00⁰0, 11¹0-01¹0, 20⁰0-00⁰0, 21¹0-01¹0, and 30⁰0-10⁰0 of the ¹⁶O¹²C³²S isotopic species and for the 20⁰0-00⁰0 band of the ¹⁶O¹³C³²S and ¹⁶O¹²C³⁴S species. Effective band constants are given for these bands.     

Laser Stark spectroscopy of FCN

Using a CO₂ laser, Stark shifted resonances have been measured for the CF stretching fundamental (ν₃) of FCN near 9.3 μm, and for two nearby “hot” bands. The band centers measured are 1076.492007 ± 0.000013 cm^?1 for 00⁰1-00⁰0, 1085.741046 ± 0.000050 cm^?1 for 01¹1-01¹0, and 1091.16222 ± 0.00015 cm^?1 for 02⁰1-02⁰0. The ground state dipole moment of FCN is found to be 2.1203 ± 0.0010 D and dipole moments are also given for the other states observed. Values are given for the rotational constant and l-doubling constant for the 01¹1 state.     

Theoretical analysis of the multi-rotational line TEA CO2 laser

A theoretical model for the multiline TEA CO₂ laser has been developed which takes into account the overlap of the P(20) line of (00⁰1) (10⁰0) regular band transition with the R(23) line of (01¹1) (11¹0) hot band transition. The model is used for the study of the influence of different parameters like laser gas temperature, gas mixture and pump rates on laser intensities of different rotational lines. This study explains the experimental results of the high power multiline TEA CO₂ laser very well.