Cavity Ring-down Absorption Spectroscopy Research Articles

Ring-down absorption spectroscopy for analytical microdevices

Ring-down absorption spectroscopy is an emerging “label-free” detection method for analytical microdevices, such as micrototal analysis systems ( μ-TAS). Developed from the related gas-phase cavity ring-down absorption spectroscopy, fiber-optic-based ring-down techniques for liquid samples offer low detection limits, high sensitivity and fast response.

Molecular Adsorption at Silica/CH3CN Interface Probed by Using Evanescent Wave Cavity Ring-Down Absorption Spectroscopy: Determination of Thermodynamic Properties

Evanescent wave cavity ring-down absorption spectroscopy is applied to measure the thermodynamic properties of the surface adsorption for neutral trans-4-[4-(dibutylamino)styryl]-1-(3-sulfopropyl) pyridinium (DP) and charged trans-4-[4-(dibutylamino)styryl]-1-methylpyridinium iodide (DMP+ I-) at the silica/CH3CN interface, where the interfacial density is determined by measurement of absorbance. The bulk concentration dependence of the surface density may be characterized with a Langmuir isotherm model, which yields saturated surface density, equilibrium constant, and free energy of adsorption of (7.0 +/- 0.3) x 10(13) cm(-2), (1.3 +/- 0.2) x 10(4) M(-1), and -23.5 +/- 0.4 kJ/mol for DP and (8.9 +/- 0.3) x 10(12) cm(-2), (2.6 +/- 0.7) x 10(4) M(-1), and -25.2 +/- 0.6 kJ/mol for DMP+ I-, respectively. The surface density of the isolated silanol groups may then be estimated in terms of the molecular probe results. The absorption contribution from the bulk solution is a factor of approximately 10(1)-10(2) smaller than the total absorbance measured such that subtraction of the bulk contribution leads to negligible change of the thermodynamic properties. The DP is adsorbed to the SiOH sites by forming hydrogen bonds, while the DMP+ cation is bound to the SiO- sites by electrostatic attraction. Surface forces are also probed by addition of triethylamine (TEA), which is competitive with DP for the silanol sites. When the TEA concentration is increased, the DP surface density is found to decrease, whereas the DMP+ surface density increases. The obtained thermodynamic properties are generally consistent with those measured by second harmonic generation spectroscopy. However, when a tetramethylammonium ((CH3)4N+ Cl-) salt is added, the DMP+ cation behaves differently between these two methods. Formation of an electrical double layer may account for the difference.

Near infrared second overtone cw-cavity ringdown spectroscopy of D 2H + ions

A study of D 2H + ions in their lowest rotational states is presented. The ions are generated in pulsed discharge in liquid N 2 cooled He/Ar/H 2/D 2 gas mixture. Near infrared (NIR) second overtone transitions in the 6534–6536 cm −1 (1.529–1.530 μm) region are used to identify the ions and determine their degree of rotational excitation. The data were obtained using NIR cavity ringdown absorption spectroscopy (NIR-CRDS). The sensitivity obtained was typically 5 × 10 −9 cm −1. The measured second overtone transition frequencies are in very good agreement (better than 0.02 cm −1) with ab initio predictions. From the Doppler broadening the kinetic temperature of ions is estimated to be (220 ± 50) K. The absolute number density of D 2H + as a function of H 2/D 2 mixing ratio and time is measured.

Detection of SiH3 radicals and cluster formation in a highly H2 diluted SiH4 VHF plasma by means of time resolved cavity ring down spectroscopy

AbstractThe spatial distribution of the SiH3 radicals between the electrodes of a hydrogen diluted silane VHF plasma under thin film hydrogenated microcrystalline silicon (μc-Si:H) growth conditions has been measured using the time resolved cavity ringdown (τ-CRD) absorption spectroscopy technique. The μc-Si:H growth rate is estimated from the measured spatial SiH3 profiles using a simple model based upon diffusion controlled flux of SiH3 radicals to the electrode surface, where the SiH3 can react with the film surface. The calculated value of μc-Si:H growth rate roughly agrees with the value of the experimentally determined growth rate. This agreement implies that the SiH3 radical is the main growth contributor to the μc-Si:H growth. Furthermore, the τ-CRD reveals the growth kinetics of the clusters in the plasma by light scattering at these clusters on time scales of 1 s after the plasma ignition.

Density and production of NH and NH2 in an Ar–NH3 expanding plasma jet

The densities of NH and NH2 radicals in an Ar–NH3 plasma jet created by the expanding thermal plasma source were investigated for various source-operating conditions such as plasma current and NH3 flow. The radicals were measured by cavity ringdown absorption spectroscopy using the (0,0) band of the AΠ3←XΣ−3 transition for NH and the (0,9,0)-(0,0,0) band of the ÃA12←X̃B12 transition for NH2. For NH, a kinetic gas temperature and rotational temperature of 1750±100 and 1920±100K were found, respectively. The measurements revealed typical densities of 2.5×1012cm−3 for the NH radical and 3.5×1012cm−3 for the NH2 radical. From the combination of the data with ion density and NH3 consumption measurements in the plasma as well as from a simple one-dimensional plug down model, the key production reactions for NH and NH2 are discussed.

Continuous-wave cavity ringdown absorption spectroscopy with a swept-frequency laser: rapid spectral sensing of gas-phase molecules

A cavity ringdown spectrometer, based on a continuous-wave swept-frequency laser, enables efficient, rapid recording of wide-ranging absorption spectra as characteristic spectral signatures of airborne molecules. The rapidly swept laser frequency resonates with the longitudinal modes of the ringdown cavity, effectively sampling the absorption spectrum of an intracavity gas at intervals defined by the cavity's free spectral range and generating a full absorption spectrum within a single rapid sweep of the widely tunable laser frequency. We report a new analog detection scheme that registers a single data point for each buildup and ringdown decay event without logging details of the full signal waveform; this minimizes demand on digitizer speed and memory depth, reducing the time scale of data processing. This results in a compact, robust, easy-to-use instrument that offers fresh prospects for spectroscopic sensing of trace species in the atmosphere.

Continuous-wave cavity ringdown spectroscopy of the 8ν polyad of water in the 25195−25340cm−1 range

State-of-the-art experiments and calculations are used to record and assign the data obtained in the weakly absorbing blue energy region of the H2O spectrum. Continuous-wave cavity ringdown absorption spectroscopy with Doppler resolution is used to probe the range from 25,195 to 25,470 cm(-1) with an absorption sensitivity of approximately 1 parts per 10(9) (ppb)/cm. 62 lines of the polyad nu(OH)=8 are reported, of which 43 are assigned using variational nuclear calculations. The study includes absorption line intensities (in the range of 10(-28)-10(-26) cmmolecule) for all lines and self-broadening pressure coefficient for a few lines. The newly obtained energy levels are also reported.

Quasi-Ice Monolayer on Atomically Smooth AmorphousSiO2at Room Temperature Observed with a High-Finesse Optical Resonator

The structure of an H(2)O monolayer bound to atomically smooth hydroxylated amorphous silica is probed under ambient conditions by near-infrared evanescent-wave cavity ring-down absorption spectroscopy. Employing a miniature monolithic optical resonator, we find sharp (approximately 10 cm(-1)) and polarized (>10:1) vibration-combination bands for surface OH and adsorbed H(2)O, which reveal ordered species in distinct local environments. Indicating first-monolayer uniqueness, the absorption bands for adsorbed H(2)O show intensity saturation and line narrowing with completion of one monolayer. Formation of the ordered H(2)O monolayer likely arises from H bonding to a quasicrystalline surface OH network.

Br 2 elimination in 248-nm photolysis of CF2Br2 probed by using cavity ring-down absorption spectroscopy

By using cavity ring-down absorption spectroscopy technique, we have observed the channel of Br2 molecular elimination following photodissociation of CF2Br2 at 248 nm. A tunable laser beam, which is crossed perpendicular to the photolyzing laser beam in a ring-down cell, is used to probe the Br2 fragment in the B 3Piou+-X1Sigmag+ transition. The vibrational population is obtained in a nascent state, despite ring-down time as long as 500-1000 ns. The population ratio of Br2(v=1)/Br2(v=0) is determined to be 0.4+/-0.2, slightly larger than the value of 0.22 evaluated by Boltzmann distribution at room temperature. The quantum yield of the Br2 elimination reaction is also measured to be 0.04+/-0.01. This work provides direct evidence to support molecular elimination occurring in the CF2Br2 photodissociation and proposes a plausible pathway with the aid of ab initio potential-energy calculations. CF2Br2 is excited probably to the 1B1 and 3B2 states at 248 nm. As the C-Br bond is elongated upon excitation, the coupling of the 1A'(1B1) state to the high vibrational levels of the ground state X 1A'(1A1) may be enhanced to facilitate the process of internal conversion. After transition, the highly vibrationally excited CF2Br2 feasibly surpasses a transition barrier prior to decomposition. According to the ab initio calculations, the transition state structure tends to correlate with the intermediate state CF2Br+Br(CF2Br...Br) and the products CF2+Br2. A sequential photodissociation pathway is thus favored. That is, a single C-Br bond breaks, and then the free-Br atom moves to form a Br-Br bond, followed by the Br2 elimination. The formed Br-Br bond distance in the transition state tends to approach equilibrium such that the Br2 fragment may be populated in cold vibrational distribution. Observation of a small vibrational population ratio of Br2(v=1)Br2(v=0) agrees with the proposed mechanism.

Threshold ionization mass spectrometry of reactive species in remote Ar∕C2H2 expanding thermal plasma

Triple stage threshold ionization mass spectrometry is successfully implemented in an Ar∕C2H2 expanding thermal plasma setup. More than 20 hydrocarbon radicals and molecules formed in the plasma, including for example the C2H, C3, C3H, and C3H2 radicals or C3H4 or C4H2 molecules, are measured and their absolute densities are determined. Thanks to a careful design, a high sensitivity of the instrument is achieved and species with densities as low as 1×1016m−3 can be detected. Issues related to the absolute density calibration procedure are considered. The proper determination of the background signal by means of a beam chopper and the influence of the chopper on the measurement are discussed and the possible composition distortion of the sampled beam due to the collisions in the sampling orifice is checked. Furthermore, reported values of electron impact ionization cross sections of hydrocarbon species are compared and, based on their similarity in the near threshold energy region, the C2H2 electron impact ionization cross section is proposed as a reasonable approximation for other hydrocarbon radicals. The results for C, CH, and C2 radicals are compared with previous cavity ringdown absorption spectroscopy measurements and a good agreement is obtained.

Molecular elimination of Br2 in 248 nm photolysis of bromoform probed by using cavity ring-down absorption spectroscopy.

By using cavity ring-down spectroscopy technique, we have observed the channel leading to Br(2) molecular elimination following photodissociation of bromoform at 248 nm. A tunable laser beam, which is crossed perpendicular to the photolysis laser beam in a ring-down cell, is used to probe the Br(2) fragment in the B(3)Pi(ou)(+)-X(1)Sigma(g)(+) transition using the range 515-524 nm. The ring-down time lasts 500 ns, so the rotational population of the Br(2) fragment may not be nascent nature, but its vibrational population should be. The vibrational population ratio of Br(2)(upsilon=1)/Br(2)(upsilon=0)=0.8+/-0.2 implies that the fragmented Br(2) is vibrationally hot. The quantum yield of the molecular elimination reaction is 0.23+/-0.05, consistent with the values of 0.26 and 0.16 reported in 234 and 267 nm photolysis of bromoform, respectively, using velocity ion imaging. A plausible photodissociation pathway is proposed, based upon this work and ab initio calculations. The A(1)A(2), B(1)E, and C(1)A(1) singlet states of bromoform are probably excited at 248 nm. These excited states may couple to the high vibrational levels of the ground state X(1)A(1) via internal conversion. This vibrationally excited bromoform readily surpasses a reaction barrier 389.6 kJ/mol prior to decomposition. The transition state structure tends to correlate with vibrationally hot Br(2). Dissociation after internal conversion of the excited states to vibrationally excited ground state should result in a large fraction of the available energy to be partitioned in vibrational states of the fragments. The observed vibrationally hot Br(2) fragment seems to favor the dissociation pathway from high vibrational levels of the ground state. Nevertheless, the other reaction channel leading to a direct impulsive dissociation from the excited states cannot be excluded.

D 2 ← D 0 transition of the anthracene cation observed by cavity ring-down absorption spectroscopy in a supersonic jet

In an attempt to contribute to the explanation of the diffuse interstellar bands (DIBs), we have studied the absorption spectrum of the anthracene cation (An +) in a supersonic jet by cavity ring-down spectroscopy. The D 2 ← D 0 transition of An + has been located at 708.76 ± 0.13 nm. This means that the same transition observed in an argon matrix is redshifted by 13.65 nm. Although the band position determined in the laboratory coincides with the position of a weak feature in the DIB spectrum, the measured width is too broad to comply with the astronomical observation.

Cavity ring-down absorption and laser-induced fluorescence for quantitative measurements of CH radicals in low-pressure flames

The absolute, quantitative spatially resolved distribution of CH radicals was measured in the reaction zone of a low-pressure methane/air flame (25 Torr) using a combination of laser-induced fluorescence (LIF) and cavity ring-down (CRD) absorption spectroscopy operating on the A 2Δ–X 2Π(0,0) transition. The spatially resolved 1-D image of LIF provides a direct measure of the CH distribution along the path of the laser beam in the CRD cavity. The temperature distribution was determined from measurements on a pair of rotational transitions. A series of LIF line images and CRD absorption measurements taken at various burner heights are combined to form a quantitative 2-D image of the CH distribution. This is used to interpret the CRD measurements along this inhomogeneous path. The 10 ppm peak CH concentration measured here on the centerline of the flame is in good agreement (within 15%) with earlier CH A–X LIF measurements calibrated by Rayleigh and Raman scattering. A 1-D LIF image collected simultaneously with CRD absorption was also used to quantify and optimize the spatial resolution of the CRD measurement.

Cavity ring-down measurements of seeded NO in premixed atmospheric-pressure H2/air and CH4/air flames

Quantitative aspects of using cavity ring-down absorption spectroscopy near 226 nm for measurements of NO mole fractions in premixed atmospheric-pressure flames are discussed. Measurements in methane–air flames showed strong broadband absorption near 226 nm by hot CO2 molecules, precluding using the cavity ring-down method in these flames at atmospheric pressure. In hydrogen–air flames, the broadband absorption at this wavelength was substantially lower. Absorption cross sections derived from non-seeded cavity ring-down spectra suggest that absorption by water is the major contribution to the background in these flames. The detectability limit for NO by cavity ring-down measurements in hydrogen–air flames using the current setup is estimated to be ∼10 ppm. Effects of the cold boundary layer on the measured NO mole fraction were accounted for by measuring the radial distributions of temperature and NO mole fraction using coherent anti-Stokes Raman scattering and laser-induced fluorescence (LIF), respectively. Measurements performed in seeded stoichiometric and lean hydrogen–air flames showed no reburning at temperatures above 1750 K, demonstrating the adequacy of using these flames for calibration of LIF measurements. At lower temperatures, the mole fraction of NO in the hot gases was up to 30% lower than that expected from the degree of seeding in the cold gases.

Number density and temperature of acetylene in hot-filament and arc-jet activated CH 4/H 2 gas mixtures measured using diode laser cavity ring-down absorption spectroscopy

Continuous-wave cavity ring-down spectroscopy (CW-CRDS) with an external cavity diode laser has been used to make diagnostic measurements of acetylene absorption in hot-filament and DC-arc plasma jet reactors operating with 1% CH 4 in H 2 and ≤0.8% CH 4/H 2 in excess Ar, respectively, and used for diamond chemical vapour deposition. The acetylene was widely distributed throughout the reactor, extending well beyond the regions of highest thermal activation as a result of diffusion processes. The average acetylene concentration was determined as (2.9±0.6)×10 13 molecules cm −3 in the hot filament reactor and (1.2±0.2)×10 14 molecules cm −3 in the DC arc jet reactor, accounting for ∼1.7% and 40% of the total C budget in the respective cases. The average acetylene gas temperature along the viewing column was 550±150 K in both environments. Variations in the concentration and temperature of acetylene with the gas feed composition and input power processing conditions for the two reactors are presented. The experiments demonstrate the effectiveness of near-IR diode laser CRDS as a probe of highly luminous environments.

Swept-Cavity Ringdown Absorption Spectroscopy: Put Your Laser Light In and Shake It All About

Cavity ringdown (CRD) absorption spectroscopy with continuous-wave (cw) tunable coherent light sources provides a convenient, sensitive, and precise way to measure very weak optical absorption spectra and to analyze trace gas concentrations. Several recently introduced innovations in cw-CRD spectroscopy are described. Our approach involves one or more single-mode tunable diode laser sources, a rapidly swept ringdown cavity, and a simple optical heterodyne detected approach (based on the dynamics of coherent light reflected from such an active optical cavity). This offers high performance in a relatively simple, low-cost, compact instrument that is facilitated by fibre optic and other standard photonics or telecommunications components. New experimental results are reported, comprising CRD spectra of water vapour in the 0.815 µm wavelength region and of mixtures of CO2 and CO in the range of 1.56–1.59 µm. Promising applications of such techniques include chemical analysis of trace gases in medicine, agriculture, industry, and the environment.

Fiber-loop ring-down spectroscopy

Pulsed, visible and near-infrared laser light is coupled into an optical fiber, which is wound into a loop using a fiber splice connector. The light pulses traveling through the fiber-loop are detected using a photomultiplier detector. It is found that once the light is coupled into the fiber it experiences very little loss and the light pulses do a large number of round trips before their intensity is below the detection threshold. Measurements of the loss-per-pass and of the ring-down time allow for characterization of the different loss mechanisms of the light pulses in the fiber and splice connector. This method resembles “cavity ring-down absorption spectroscopy” and is well suited to characterize low-loss processes in fiber optic transmission independent from power fluctuations of the light source. It is demonstrated that by measuring the ring-down times one can accurately determine the absolute transmission of an optical fiber and of the fiber connector. In addition it is demonstrated that the technique is useful as an absorption spectroscopic technique of very small sample volumes. A solution of an organic dye was placed between the fiber ends instead of the usual index matching fluid, and an absorption spectrum of 7×10−15 mol of the dye 1,1′-diethyl-4,4′-dicarbocyanine iodide in 7×10−12 L of dimethylsulfoxide was recorded.

Rapidly swept, continuous-wave cavity ringdown spectroscopy with optical heterodyne detection: single- and multi-wavelength sensing of gases

Spectroscopic sensing of gases can be performed with high sensitivity and photometric precision by cavity ringdown (CRD) absorption spectroscopy. Our cavity ringdown spectrometer incorporates continuous-wave (cw) tunable diode lasers, fibre-optic coupling and standard photonics and optical telecommunications components. It comprises a rapidly swept optical cavity in a single-ended optical heterodyne transmitter–receiver configuration, enabling optical absorption of gases to be recorded either as single-frequency scanned spectra or as simultaneous, multi-wavelength tailored spectra. By measuring weak near-infrared rovibrational spectra of carbon dioxide gas (CO2), with high resolution in the vicinity of 1.53 μm, we have realised a noise-limited absorption sensitivity of 2.5×10-9 cm-1 Hz-1/2. Analytical sensitivity limits (both actual and projected) and prospective gas-diagnostic applications are discussed. Our approach to cw-CRD spectroscopy offers high performance in a relatively simple, low-cost, compact instrument that is amenable to chemical analysis of trace gases in medical, agricultural, industrial and environmental situations.

Observation of lithium dimers in laser produced plume by cavity ring-down spectroscopy

Laser ablation of solid lithium with 308 nm excimer laser is performed. Cavity ring-down absorption spectroscopy is used to detect atoms and molecules in the plume. They are observed at given distances from the target depending on different time delay from vaporization and observation window width. Large ratio of dimer to atom densities is observed compared to the thermalized vapor. Fast dimers appear with rovibrational temperatures about 175 K. Slow dimers exhibit non-Boltzmann rovibrational distribution in which large rotational numbers are preferred.

Quasi-simultaneous detection of CH 2 O and CH by cavity ring-down absorption and laser-induced fluorescence in a methane/air low-pressure flame

The combination of two-dimensional, planar laser-induced fluorescence (PLIF) and cavity ring-down (CRD) absorption spectroscopy is applied to map quantitatively the spatial distributions of CH2O and CH in a methane/air flame at 25 Torr. Both species are detected in the same spectral region using the overlapping CH2O A 1 A 2 -X 1 A 1 41 0 and CH B-X(1,0 )bands. The combination of diagnostic techniques exploits the spatial resolution of LIF and the quantitative CRD absorption measure of column density. The spatially resolved PLIF provides the distribution of absorbers and line-of-sight CRD absorption the absolute number density needed for quantitative concentration images. The peak CH2O concentration is (3.5±1.4 )×1014 cm-3, or 1450±550 ppm at 1000 K. The lack of precise absorption cross-section data produces these large error limits. Although a flame model predicts lower amounts, these large uncertainties limit this measurement’susefulness as a test of the flame chemistry.