Cavity Ring-down Detection Research Articles

Step-modulated decay cavity ring-down detection for double resonance spectroscopy.

A method of measuring double resonant two-photon signal and background from a single cavity ring-down decay is introduced. This is achieved by modulating the double resonance loss via one of the light sources exciting the transition. The noise performance of the method is characterized theoretically and experimentally. The addition of a new parameter to the fitting function introduces a minor noise increase due to parameter correlation. However, the concurrent recording of the background can extend the stable measurement time. Alternatively, the method allows a faster measurement speed, while still recording the background, which is often advantageous in double resonance measurements. Finally, the method is insensitive to changes in the cavity decay rate at short timescales and can lead to improved performance if they have significant contribution to the final noise level compared to the detector noise.

Quantitative Mid-Infrared Cavity Ringdown Detection of Methyl Iodide for Monitoring Applications.

Methyl iodide is a toxic halocarbon with diverse industrial and agricultural applications, and it is an important ocean-derived trace gas that contributes to the iodine burden of the atmosphere. Quantitative analysis of CH3I is mostly based on gas chromatography coupled with mass spectrometry or electron capture detection (GC-MS/ECD) as of yet, which often limits the ability to conduct in situ high-frequency monitoring studies. This work presents an alternative detection scheme based on mid-infrared continuous wave cavity ringdown spectroscopy (mid-IR cw-CRDS). CH3I was detected at the RR2(15) rovibrational absorption transition at ṽ = 3090.4289 cm-1; part of the corresponding v4 vibration band has been measured with Doppler-limited resolution for the first time. A line strength of S(T = 295 K) = (545 ± 20) cm/mol, corresponding to a line center absorption cross-section σc(p = 0 bar) = (1.60 ± 0.06) × 105 cm2/mol, and pressure-broadening coefficients γp(Ar) = (0.094 ± 0.002) cm-1/bar and γp(N2) = (0.112 ± 0.003) cm-1/bar have been determined. The performance of the detection system has been demonstrated with a tank-purging experiment and has been directly compared with a conventional GC-MS/ECD detection system. Quantitative detection with high reproducibility and continuous sampling is possible with a current noise-equivalent limit of detection of 15 ppb at 20 mbar absorption-cell pressure and 70 s averaging time. This limit of detection is suitable for practical applications in the ppm mixing ratio level range such as workplace monitoring, leak detection, and process studies. Natural environmental abundances are much lower, therefore possibilities for future improvement of the detection limit are discussed.

Detection of S-nitroso compounds by use of midinfrared cavity ring-down spectroscopy.

S-Nitroso compounds have received much attention in biological research. In addition to their role as nitric oxide donors, there is growing evidence that these compounds are involved in signaling processes in biological systems. Determination of S-nitrosylated proteins is of great importance for fundamental biological research and medical applications. The most common method to assay biological S-nitroso compounds is to chemically or photochemically reduce SNO functional groups to release nitric oxide, which is then entrained in an inert gas stream and detected, usually through chemiluminescence. We report a method of S-nitroso compound detection using cavity ring-down measurements of gaseous NO absorbance at 5.2 μm. The proposed method, in contrast to the chemiluminescence-based approach, can be used to distinguish isotopic forms of NO. We demonstrated sensitivity down to ∼2 pmol of S(14)NO groups and ∼5 pmol of S(15)NO groups for S-nitroso compounds in aqueous solutions. The wide dynamic range of cavity ring-down detection allows the measurement of S-nitroso compound levels from pico- to nanomole amounts.

Following Radical Pair Reactions in Solution: A Step Change in Sensitivity Using Cavity Ring-Down Detection

The study of radical pair intermediates in biological systems has been hampered by the low sensitivity of the optical techniques usually employed to investigate these highly reactive species. Understanding the physical principles governing the spin-selective and magneto-sensitive yields and kinetics of their reactions is essential in identifying the mechanism governing bird migration, and might have significance in the discussion of potential health hazards of electromagnetic radiation. Here, we demonstrate the powerful capabilities of optical cavity-enhanced techniques, such as cavity ring-down spectroscopy (CRDS) in monitoring radical recombination reactions and associated magnetic field effects (MFEs). These include submicrosecond time-resolution, high sensitivity (baseline noise on the order of 10(-6) absorbance units) and small (μL) sample volumes. Combined, we show that these represent significant advantages over the single-pass flash-photolysis techniques conventionally applied. The studies described here focus on photoinduced radical pair reactions involving the protein lysozyme and one of two possible photosensitizers: anthraquinone-2,6-disulphonate and flavin mononucleotide. CRDS-measured MFEs are observed in pump-probe experiments and discussed in terms of the sensitivity gains and sample-volume minimization afforded by CRDS when compared with flash photolysis methods. Finally, CRDS is applied to an in vitro MFE study of intramolecular electron transfer in the DNA-repair enzyme, Escherichia coli photolyase, a protein closely related to cryptochrome which has been proposed to mediate animal magnetoreception.

Evanescent-wave cavity ring-down detection of cytochrome c on surface-modified prisms

Adsorption kinetics and molecular interactions on different surface interfaces are studied by means of evanescent-wave cavity ring-down spectroscopy, using total internal reflection surfaces onto which different self-assembled monolayers are covalently attached. The adsorption of cytochrome c (a positively charged, spherical heme protein) to a negatively charged bare silica surface, as well as to C 18-coated (hydrophobic) and C 3NH 2-coated (positively charged) silica have been studied. It is experimentally verified that these surface layers do not interfere with the sensitive measurement of adsorbed cyt c monolayers using the evanescent wave in a ring-down scheme. Attaching monolayers covalently to the silica total internal reflection surface is a first step towards the development of a biosensor that makes use of immobilized biomolecules for specific detection of analytes in solution.

Continuous-wave cavity-ringdown detection of stimulated Raman gain spectra

Cavity ringdown (CRD) spectroscopy, with its high sensitivity, provides a novel way to perform continuous-wave (cw) stimulated Raman gain (SRG) spectroscopy, rather than by conventional optically detected coherent Raman techniques. Tunable cw laser light at ∼1544 nm is used to probe ringdown decay from a rapidly-swept, high-finesse optical cavity containing a gas-phase sample of interest and itself located inside the cavity of a cw single-longitudinal-mode Nd:YAG ring laser operating at ∼1064.4 nm. This approach is used to measure cw SRG spectra of the ν 1 fundamental rovibrational Raman band of methane gas at ∼2916.5 cm−1. The resulting SRG-CRD resonances have ringdown times longer than in the off-resonance case, in contrast to the usual shorter ringdown times arising from absorption and other loss processes. Previously reported noise-equivalent sensitivities have been substantially improved, by using a second ringdown cavity to facilitate subtraction of infrared-absorption background signals. Moreover, by employing a ringdown cavity in the form of a ring, the SRG-pump and CRD-detected Stokes beams can co-propagate uni-directionally, which significantly reduces Doppler broadening.

Continuous-wave stimulated Raman gain spectroscopy with cavity ringdown detection

Cavity ringdown (CRD) spectroscopy is extended for the first time from its conventional optical-absorption mode of operation into the regime of coherent Raman spectroscopy. Continuous-wave (cw) stimulated Raman gain (SRG) spectra of the 2916.5-cm-1 ν1 rovibrational fundamental Raman band of methane (CH4) gas are measured, using tunable cw laser light at ∼1544 nm to probe ringdown decay from a rapidly swept optical cavity that is itself inside the cavity of a cw single-longitudinal-mode Nd:YAG ring laser operating at ∼1064.5 nm. The resulting change of ringdown decay rate is dependent on pump laser irradiance and is associated with Raman gain. Remarkably, such SRG-CRD resonances display ringdown times that are longer than in the off-resonance case, contrasting with the usual reduction of ringdown time associated with absorption and other loss processes.

Phase-shift cavity ring-down spectroscopy to determine absolute line intensities

Cavity ring-down detection techniques can sensitively determine frequency-dependent absorption cross-sections of gasses. However, so-called line-width problems and amplified spontaneous emission of the laser light source lowers the technique’s quantitative accuracy. Using phase-shift cavity ring-down spectroscopy (PSCRD), we measured absolute line intensities of the spin-forbidden transitions in the b 1 Σ g + ( ν ′ = 0 ) ← X 3 Σ g - ( ν ″ = 0 ) band of molecular oxygen. Our results were within 4% of values obtained from the HITRAN database, demonstrating the accuracy of PSCRD, when corrected for amplified spontaneous emission. Its high sensitivity (2 × 10 −8 cm −1), simplicity and high duty cycle make PSCRD a powerful diagnostic technique.

Cavity ringdown detection of losses in thin films in the telecommunication wavelength window

The method of cavity ringdown spectroscopy (when a tunable pulsed optical parametric oscillator was used) was extended for the loss evaluation in thin films (2-20-microm thickness). The technique was applied in two key telecommunication wavelength ranges of 1260-1330 and 1480-1650 nm. The measurement sensitivity was determined to be 50 ppm (5 x 10(-5)). The results for polymer films are in close correlation with conventional spectrophotometric data and propagation loss for planar waveguides. Films of greater thickness and better optical quality are expected to provide an even higher loss resolution.