Near-infrared cavity enhanced absorption spectroscopy of hot water and OH in an oven and in flames

A compact diode laser operating around 1.5 μm was used to measure cavity enhanced absorption spectra of hot water molecules and OH radicals in radiative environments under atmospheric conditions. Spectra of air were measured in an oven at temperatures ranging from 300 K to 1500 K. These spectra contained rovibrational lines from water and OH. The water spectra were compared to simulations from the HITRAN and HITEMP databases. Furthermore, spectra were recorded in the flame of a flat methane/air burner and in an oxyacetylene flame produced by a welding torch. The results show that cavity enhanced absorption spectroscopy provides a sensitive method for rapid monitoring of species in radiative environments. Received: 22 February 2001 / Revised version: 23 April 2001 / Published online: 7 June 2001     

Frequency measurement of I2 lines in the NIR using Ca and CH4 optical frequency standards

2 lines have been carried out using difference-frequency mixing of the emission of CH₄ and Ca frequency standards at 88 THz (or 3.4 μm) and 456 THz (or 657 nm), respectively. A power of ≈10 pW for the mixing product at 815 nm was obtained using a critically phase-matched KTP crystal and input powers of the order of mW. The relative uncertainty of the measurement was a few times 10^-11, limited by the frequency instability of the laser source locked to I₂. Received: 3 December 1997/Revised version: 16 February 1998     

Temperature measurements in flames using water molecule overtone . spectra detected by intracavity laser absorption spectroscopy

Received: 14 June 1996 / Revised version: 6 September 1996     

Systematic analysis of the Fourier transform spectrum of CH3OH between 400 and 950 cm

We have investigated a high-resolution Fourier transform (FT) absorption spectrum of the ¹³CH₃OH isotopomer of methanol from 400 to 950 cm⁻¹ with the “Ritz” program. We present the assignments of 7160 transitions, 3021 of which belong to A-symmetry, and 4139 to E-symmetry. These transitions occur between states labeled by K quantum numbers up to 14, and by torsional quantum numbers n up to 4. The “Ritz” program evaluated the energies of the 4684 involved levels with an accuracy of the order of 10⁻⁴ cm⁻¹. All of the assigned lines correspond to transitions involving torsionally excited levels within the ground small-amplitude vibrational state.     

Cavity ring-down spectroscopy of OH radicals in low pressure flame

10 molecules/cm³) and large dynamic range (more than 20 000) are demonstrated. CRDS also provides accurate temperature measurements, with statistical errors less than 2%. Measured concentration profiles are in reasonable agreement with calculated values. It is observed that in the preflame zone (where the temperature is about 1000 K), the OH concentration at the first vibrational excited state is about seven times larger than the equilibrium OH(v”=1) concentration at this temperature. Received: 24 June 1997/Revised version: 12 September 1997     

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     

Wave packet dynamics in different electronic states investigated by femtosecond time-resolved four-wave-mixing spectroscopy

This paper reviews results on wave packet dynamics investigated by means of femtosecond time-resolved four-wave-mixing (FWM) spectroscopy. First, it is shown that by making use of the various degrees of freedom which are offered by this technique information about molecular dynamics on different potential-energy surfaces can be accessed and separated from each other. By varying the timing, polarization, and wavelengths of the laser pulses as well as the wavelength of the detection window for the FWM signal, different dynamics are coherently excited and probed by the nonlinear spectroscopy. As a model system we use iodine in the gas phase. These techniques are then applied to more-complex molecules (gas phase: benzene, toluene, a binary mixture of benzene and toluene; solid state: polymers of diacetylene matrix-isolated in single crystals of monomer molecules). Here, ground-state dynamics are investigated first without any involvement of electronically excited states and then in electronic resonance to an absorption transition in the investigated molecules. Signal modulations result which are due to wave packet motion as well as polarization beats between modes in different molecules. Phase and intensity changes yield information about intramolecular vibrational energy redistribution, population decay (T₁), phase relaxation (T₂), and coherence times. Received: 12 October 1999 / Published online: 13 July 2000     

Power-boosted difference-frequency source for high-resolution infrared spectroscopy

We analyzed the spectroscopic performance of a difference-frequency source that utilizes a 5-W Yb-fiber amplifier for the “signal” radiation in order to increase the “idler” power generated around 4.3 μm. The amplifier is seeded by a monolithic-cavity Nd:YAG laser at 1064 nm. The intensity noise spectral density of the “idler” radiation was characterized. Cavity-enhanced saturated-absorption spectroscopy was also performed to test the frequency resolution. In particular, we observed the Lamb-dip spectrum of the ro-vibrational (00⁰0-00⁰1)R(0)transition of ¹⁷O¹²C¹⁶O in natural abundance. To our knowledge, this is the first observation of that transition by the Lamb-dip technique. Received: 19 December 2002 / Revised version: 3 February 2003 / Published online: 16 April 2003 RID="*" ID="*"Corresponding author. Fax: +39-055/4572-451, E-mail: mazzotti@inoa.it     

Absolute frequency measurement of a CO2/OsO4 stabilized laser at 28.8 THz

A cw carbon dioxide laser operating on the 10 μm R(0)_I transition (28.832 THz) was frequency stabilized by a servo lock to the saturated absorption dip of the Q(15) transition of ¹⁸⁸OsO₄. The laser frequency was measured with a cesium-clock-based frequency chain. In addition, the absorption line frequencies Q(14) of ¹⁸⁸OsO₄ and sQ(4,3) of ¹⁵NH₃, were measured relative to the frequency of Q(15). Received: 21 August 2000 / Revised version: 15 January 2001 / Published online: 30 March 2001     

The analysis of the precision of single shot 2λ-CARS temperature measurements in hydrogen

Received: 16 October 1996/Revised version: 17 March 1997     

Diode laser spectroscopy using two modes of an InAsSb/InAsSbP laser near 3.6 μm

A new type of multimode semiconductor laser, based on InAsSb/InAsSbP heterostructures, is described. This continuous laser working in a broad range of temperatures (30–100 K) was tested using a closed-cycle He-cryostat and its quality was demonstrated using the laser spectroscopy of gases absorbing in the 2800 cm^-1 region. Two different laser modes were used to increase the spectral range. The spectral characteristics and tunability of the laser were explored as a function of heat-sink temperature and drive current with the aim of developing its use for high–resolution spectroscopy. The laser has potential applications in the field of chemistry, atmospheric research and the study of the kinetics of reactive species. Received: 18 October 1999 / Revised version: 10 May 2000 / Published online: 16 August 2000     

Size-selected, supported clusters: the interaction of carbon monoxide with nickel clusters

We report on the size-dependent chemical reactivity of nickel clusters with up to 30 atoms. Monodispersed Ni₃₀ clusters show a higher reactivity for CO dissociation than Ni₁₁ and Ni₂₀. Under our experimental conditions the smallest nickel clusters (Ni_x, x<4) produce nickelcarbonyl complexes. These results demonstrate that such small clusters are unique for catalytic reactions not only due to their high surface-to-volume ratio but also essentially because of the distinctive properties of different cluster sizes. In addition thermal desorption spectroscopy of CO shows that on average four molecules are weakly adsorbed per Ni₁₁ at saturation coverage. Using an isotopic mixture of ¹²CO and ¹³CO, infrared spectroscopy reveals the existence of a vibrational coupling interaction between the four COs. A semi-classical model of interacting dipoles is applied to correlate the observed vibrational frequency shifts with the arrangement of the COs on the cluster. This simple analysis favors a three-dimensional structure for the deposited clusters. Received: 23 March 1998/Accepted: 25 August 1998     

Remote sensing of volcanic gases with a DFB-laser-based fiber spectrometer

We demonstrate monitoring of H₂O and CO₂ emitted in a volcanic area, using a spectrometer equipped with two distributed feedback (DFB) semiconductor diode lasers. Each laser is resonant with a molecular species and is fiber-coupled to allow remote operation of the spectrometer. Recordings of H₂O and CO₂ lines made at the Solfatara volcano, in southern Italy, are shown, and the application of such a spectrometer as a new tool for the continuous monitoring and surveillance of volcanoes is discussed. Received: 28 June 1999 / Revised version: 20 December 1999 / Published online: 23 February 2000     

On the accurate determination of pressure- induced line shifts in the 2ν<Subscript>3</Subscript> band of H<Subscript>2</Subscript>O at 1320 nm

A simple technique is demonstrated for the accurate determination of pressure-induced line shifts of water in air. High- and low-pressure water samples are simultaneously probed on selected overtone transitions at 1.32 μm using a current-modulated distributed-feedback diode laser and harmonic detection. The resultant profiles yield an average line shift of -293±30 MHz/atm for the 3,3,0 (002)2,2,1 (000)transition at 227251 GHz and -134±7 MHz/atm for the 3,2,1 (002)2,1,2 (000) transition at 227027 GHz. Comparisons are made between first- and second-harmonic detection, and wavelength- and frequency-modulation regimes. The effect of modulation broadening on the returned line shifts is quantified. Received: 12 August 2002 / Revised version: 21 October 2002 / Published online: 8 January 2003 RID="*" ID="*"Corresponding author. Fax: +44-01865/275410, E-mail: gus.hancock@chemistry.ox.ac.uk     

Application of spontaneous Raman and Rayleigh scattering and 2D LIF for the characterization of a turbulent CH4/H2/N2 jet diffusion flame

4 /H₂/N₂ diffusion flame. Important aspects of the measuring technique, such as accuracy, cross talk between different Raman bands, and the correction procedure for background from laser-induced fluorescence are discussed. In addition, a 2D LIF and Rayleigh imaging system were used to study the structures of OH, CH, NO, and temperature distributions in the flame. A comparison between two different CH detection schemes is presented. A main goal of the investigations was a detailed and accurate characterization of the investigated flame as well as the study of experimental techniques. Joint pdfs of the temperature and major species concentrations were determined at nearly 100 measuring locations covering the complete flame. Parts of the results are presented in the paper in order to discuss effects of differential diffusion, flame extinction, and interaction between flow field and chemistry. The measured data sets which are available on the Internet are well suited for testing and validating mathematical flame models. Received: 8 July 1997/Revised version: 23 October 1997     

Open-path trace gas detection of ammonia based on cavity-enhanced absorption spectroscopy

A compact open-path optical ammonia detector is developed. A tunable external-cavity diode laser operating at 1.5 μm is used to probe absorptions of ammonia via the cavity-enhanced absorption (CEA) technique. The detector is tested in a climate chamber. The sensitivity and linearity of this system are studied for ammonia and water at atmospheric pressure. A cluster of closely spaced rovibrational overtone and combination band transitions, observed as one broad absorption feature, is used for the detection of ammonia. On these molecular transitions a detection limit of 100 ppb (1 s) is determined. The ammonia measurements are calibrated independently with a chemiluminescence monitor. Compared to other optical open-path detection methods in the 1–2 μm region, the present result shows an improved sensitivity for contactless ammonia detection by over one order of magnitude. Using the same set-up, a detection limit of 100 ppm (1 s) is determined for the detection of water at atmospheric pressure. Received: 19 January 2000 / Revised version: 6 March 2000 / Published online: 7 June 2000     

Ultra-sensitive mid-infrared cavity leak-out spectroscopy using a cw optical parametric oscillator

We report a portable, all-solid-state, mid-infrared spectrometer for trace-gas analysis. The light source is a continuous-wave optical parametric oscillator based on PPLN and pumped by a Nd:YAG laser at 1064 nm. The generated single-frequency idler output covers the wavelength region between 2.35 and 3.75 μm. With its narrow line width, this light source is suitable for precise trace-gas analysis with very high sensitivity. Using cavity leak-out spectroscopy we achieved a minimum detectable absorption coefficient of 1.2×10^-9 /cm (integration time: 16 s), corresponding, for example, to a detection limit of 300 parts per trillion ethane. This sensitivity and the compact design make this trace-gas analyzer a promising tool for various in situ environmental and medical applications. Received: 19 September 2002 / Published online: 15 November 2002 RID="*" ID="*"Corresponding author. Fax: +49-228/733-474, E-mail: frank.kuehnemann@iap.uni-bonn.de     

Pressure dependence of vibrational Raman scattering of narrow-band, 248-nm, laser light by H2, N2, O2, CO2, CH4, C2H6, and C3H8 as high as 97 bar

We have previously investigated methods that image high-pressure processes such as combustion inside automobile cylinders and aircraft engines, or chemical phenomena in supercritical fluids. Here we show that vibrational Raman scattering can simply obtain, quantitatively, densities of some combustion-relevant molecules. We use narrow-band KrF excimer-laser light. Measurements for H₂, N₂, O₂, CO₂, and CH₄ are in the pressure range from 1 to 60 bar, whereas those for C₂H₆ and C₃H₈ are up to their respective vapor pressures. All these species are at ambient temperature. Additional measurements are described for CO₂ up to 96.8 bar and 318 K, where CO₂ is a supercritical fluid. The O₂ measurements are complicated by a photochemical formation of O₃; those in supercritical CO₂ by drastic bending of the laser beam within this medium. We show that, for each gas, the Raman signal is directly proportional to gas density, thereby making quantitative analysis particularly convenient. For each species, we present an estimate of its Raman cross-section relative to that of N₂. However we recommend that future diagnostics users calibrate their own systems for relative species sensitivity. Received: 23 December 1999 / Revised version: 6 June 2000 / Published online: 20 September 2000     

Differential Helmholtz resonant photoacoustic cell for spectroscopy and gas analysis with room-temperature diode lasers

The results of theoretical and experimental studies and the design of a multi-purpose differential Helmholtz resonant photoacoustic detector (DHRD) and its applications to high-resolution spectroscopy of molecular gases and gas analysis with a room-temperature diode laser in the near-IR region are summarized. The series of experiments and numerical analysis of the DHRD sensitivity were performed for both types (single-pass and multi-pass) of DHRDs within a wide pressure range 0.1–101 kPa, including the regime of a gas flowing through a DHRD cell. The hardware and electronic arrangement of DHRDs for diode laser spectrometers and gas analyzers providing a limiting absorption sensitivity better than 10^-7 Wm^-1 are described. The results of measurements of spectral line parameters of H₂O near 800 and 1390 nm and CH₄ near 1650 nm (intensities, line broadening and shifting by atomic and molecular gases) are presented and discussed. The problems and the ways of perfection of the methodology and accuracy of DHRD techniques with tunable diode lasers of near-IR and visible spectral ranges are discussed. Received: 1 April 2002 / Revised version: 20 June 2002 / Published online: 21 August 2002 RID="*" ID="*"Corresponding author. Fax: +7/382-225-8026, E-mail: kvan@asd.iao.ru     

Temperature evaluation of UF6 and cluster detection in nozzle expansion using low-resolution infrared absorption spectroscopy

6 and mixtures of UF₆ with argon and nitrogen through a bidimensional nozzle was studied using low-resolution infrared spectroscopy in the ν₃ absorption band region. The experiments were carried out in order to calculate the molecular temperature of the beam and also to verify cluster formation in the expansion. The molecular beam temperature evaluation was based on the measurements of the low-resolution bandwidth, which were compared to simulated spectra results. The temperatures were also evaluated using the measured pressure at the end of the nozzle by a pitot tube. In the conditions where no cluster formation was observed the calculated theoretical temperatures using an equilibrium expansion model are in good agreement with the data obtained through the analysis of the experimental spectra and through the pitot tube pressure measurement. Cluster formation was observed for temperatures below about 120 K. In these conditions the infrared spectra showed shoulders in the region above 630 cm^-1 and a shoulder or band between 616 and 600 cm^-1. Received: 5 January 1998/Accepted: 14 May 1998