Broadband coherent anti-Stokes Raman spectroscopy with a modeless dye laser

We develop a modeless dye laser for broadband coherent anti-Stokes Raman spectroscopy (CARS) and investigate the operational characteristics of the modeless laser. The energy efficiency of the modeless laser is 6%, and the beam divergence is 0.65 mrad. We construct a compact movable CARS system with the modeless laser and a graphite tube furnace to assess the accuracy of the CARS temperature. It is found that the difference between the averaged CARS temperature and the radiation temperature measured with an optical pyrometer is <2% at a temperature range from 1000 to 2400 K. We also measure the averaged CARS temperature drift owing to the variation of the spectral distribution of the modeless laser, which is <1.5% during 5 h of operation.     

Noise in single-shot broadband coherent anti-Stokes Raman spectroscopy that employs a modeless dye laser

The noise in single-shot coherent anti-Stokes Raman (CARS) spectroscopy that employs a broadband modeless dye laser (MDL) is examined and the results are compared with those of a conventional dye laser. The noise of the dye-laser, the nonresonant CARS, and the resonant N(2) CARS signals are determined. The use of a MDL is shown to result in substantially reduced CARS noise when the CARS signal is generated with a single-mode pump laser, but only a marginal reduction of noise is observed with a multimode pump source The noise measurements are compared with theoretical predictions that are based on models that assume modes of random amplitudes and phases in the multimode laser sources. The combination of a MDL and a single-mode pump laser is shown to increase the precision of single-shot N(2) CARS temperature measurements.     

Multiplex H2 coherent anti-Stokes Raman scattering thermometry with a modeless laser

The use of a modeless laser as the Stokes source for multiplex coherent anti-Stokes Raman scattering in molecular hydrogen is reported. The elimination of noise associated with mode competition in conventional standing wave lasers is shown to result in reliable and accurate single-shot thermometry of H(2) in a microwave-assisted diamond chemical vapor deposition plasma reactor. Single-shot temperatures are recorded with a precision of 7.3%. Possible improvements to this precision are discussed and applications of the technique for on-line process monitoring are briefly presented.     

High-resolution broadband N2 coherent anti-Stokes Raman spectroscopy: comparison of measurements for conventional and modeless broadband dye lasers

We have performed high-resolution N2 coherent anti-Stokes Raman spectroscopy (CARS) measurements using a modeless dye laser (MDL) as the Stokes beam source to determine the effects of a reduction in mode noise on the accuracy and precision of the method. These results are compared with previous research that employed a conventional broadband dye laser (CBDL) as the Stokes beam source. A new spectral-fitting procedure was developed to avoid starting-point bias in the least-squares fitting results, which possibly had altered the previous measurements. Single-shot measurements of pressure were performed in a static-pressure vessel over the range of 0.1-4.0 atm to examine the pressure sensitivity of the technique. The precision of these measurements is a measure of the baseline noise level of the system, which sets the detection limit for flow-field pressure fluctuations. Centerline measurements of pressure and temperature in an underexpanded jet (Mj = 1.85) were also used to determine the performance of the technique in a compressible flow field. Our study represents the first known application, to our knowledge, of a MDL CARS system in a low-temperature, low-pressure supersonic environment. Improvements in accuracy for mean single-shot measurements and increased precision were found for pressure vessel conditions above 1.0 atm. For subatmospheric pressure vessel conditions (0.1-1.0 atm) and the underexpanded jet measurements, there was a decrease in accuracy and precision compared with the CBDL results. A comparison with the CBDL study is included, along with a discussion of the MDL system behavior.     

Development of multipoint vibrational coherent anti-Stokes Raman spectroscopy for flame applications

A novel technique for coherent anti-Stokes Raman spectroscopy (CARS) measurements in multiple points is presented. In a multipass cavity the pump and Stokes laser beams are multiply reflected and refocused into a measurement volume with an adjustable number of separated points along a line. This optical arrangement was used in a vibrational CARS setup with planar BOXCARS phase-matching configuration. The CARS spectra from spatially separated points were recorded at different heights on a CCD camera. Measurements of temperature profiles were carried out in the burned gas zone of a premixed one-dimensional flame to demonstrate the applicability of this method for temperature measurements in high-temperature regions. The ability to measure in flames with strong density gradients was demonstrated by simultaneous measurements of Q-branch spectra of N2 and CO in a Wolfhard-Parker burner flame. Interference phenomena found in multipoint spectra are discussed, and possible solutions are proposed. Merits and limitations of the technique are discussed.     

Multiplex coherent anti-Stokes Raman spectroscopy by use of a nearly degenerate broadband optical parametric oscillator

Optical parametric oscillators (OPO's) provide low-maintenance solid-state alternatives to dye lasers. We present results from use of a nearly degenerate broadband OPO for multiplex coherent anti-Stokes Raman spectroscopy. The system described is capable of generating spectra that cover a range of approximately 1000 cm(-1).     

Towards an anthrax detector using the femtosecond adaptive spectroscopic technique for coherent anti-Stokes Raman Spectroscopy: Coherent anti-Stokes Raman spectroscopy signal from dipicolinic acid in bacterial spores

Abstract

We present experimental evidence of a resonant coherent anti-Stokes Raman spectroscopy (CARS) signal from dipicolinic acid, a marker molecule in anthrax spores. We also show some evidence of resonant CARS signal associated with the 1000 cm^?1 resonance from Bacillus Globigii spores which are similar to anthrax spores. These results constitute a first step towards developing a rapid identification technique for bacterial spores.     

Tunable excitation source for coherent Raman spectroscopy based on a single fiber laser

We demonstrate a wavelength tunable optical excitation source for coherent Raman scattering (CRS) spectroscopy based on a single femtosecond fiber laser. Electrically controlled wavelength tuning of Stokes optical pulses was achieved with soliton self frequency shift in an optical fiber, and linear frequency chirping was applied to both the pump and the Stokes waves to significantly improve the spectral resolution. The coherent anti-Stokes Raman scattering (CARS) spectrum of cyclohexane was measured and vibrational resonant Raman peaks separated by 70?cm(-1) were clearly resolved. Single laser-based tunable excitation may greatly simplify CRS measurements and extend the practicality of CRS microscopy.     

Annular phase-matched dual-pump coherent anti-stokes Raman spectroscopy system for the simultaneous detection of nitrogen and methane

The concentration and pressure dependence of dual-pump coherent anti-Stokes Raman spectroscopy (CARS) signals from nitrogen and methane was investigated. CARS spectra were acquired from a gas cell at pressures of 0.007 to 2.24 MPa and methane concentrations of 0.5 to 50%. The square root of the methane signal intensity divided by the nitrogen signal intensity was found to have a near-linear dependence on methane concentration at all pressures investigated. The pressure dependence of this integrated intensity ratio decreased with increasing pressure and became negligible at the highest pressures tested. The shot-to-shot variation at concentrations determined from single-laser-shot measurements was less than 7%. Single-laser-shot CARS spectra of nitrogen and methane were obtained from the cylinder of a firing direct-injection natural gas engine.     

Simultaneous temperature and exhaust-gas recirculation-measurements in a homogeneous charge-compression ignition engine by use of pure rotational coherent anti-Stokes Raman spectroscopy

Pure rotational coherent anti-Stokes Raman spectroscopy was used for the simultaneous determination of temperature and exhaust-gas recirculation in a homogeneous charge-compression ignition engine. Measurements were performed in a production-line four-cylinder gasoline engine operated with standard gasoline fuel through small optical line-of-sight accesses. The homogenization process of fresh intake air with recirculated exhaust gas was observed during the compression stroke, and the effect of charge temperature on combustion timing is shown. Single-pulse coherent anti-Stokes Raman spectroscopy spectra could not only be taken in the compression stroke but also during the gas-exchange cycle and after combustion. Consequently, the used method has been shown to be suitable for the investigation of two of the key parameters for self-ignition, namely temperature and charge composition.     

Measurements of temperature spatial distribution and fluctuations in a hydrogen-oxygen flame at high pressures by means of coherent anti-Stokes Raman spectroscopy

The results of measurements of the temperature field in a hydrogen-oxygen flame by means of broadband coherent anti-Stokes Raman spectroscopy are presented. The measurements were performed at pressures up to 1.7 MPa and temperatures ~3000 K with the spatial resolution of ~0.04 × 0.04 × 2.5 mm³. The duration of a single measurement was 10 ns and the sampling rate was 10 Hz. The error of the temperature determination was ~4% for the single-shot measurements and ～0.15% for the measurements of the average values during 100 s under quasi-stationary burning conditions.     

Simultaneous vibrational and pure rotational coherent anti-stokes Raman spectroscopy for temperature and multispecies concentration measurements demonstrated in sooting flames

The potential of measuring temperature and multiple species concentrations (N2, O2, CO) by use of combined vibrational coherent anti-Stokes Raman spectroscopy (CARS) and pure rotational CARS has been investigated. This was achieved with only one Nd:YAG laser and one dye laser together with a single spectrograph and CCD camera. From measurements in premixed sooting C2H4-air flames it was possible to evaluate temperatures from both vibrational CARS and rotational CARS spectra, O2 concentration from the rotational CARS spectra, and CO concentration from the vibrational CARS spectra. Quantitative results from premixed sooting C2H4-air flames are presented, and the uncertainties in the results as well as the possibility of extending the combined CARS technique for probing of additional species are discussed.     

Validation of a rotational coherent anti-Stokes Raman spectroscopy model for carbon dioxide using high-resolution detection in the temperature range 294-1143 K

Experiments were performed in the temperature range of 294-1143 K in pure CO(2) using high-resolution rotational coherent anti-Stokes Raman spectroscopy (CARS), in the dual-broadband approach. Experimental single-shot spectra were recorded with high spectral resolution using a single-mode Nd:YAG laser and a relay imaging lens system on the exit of a 1 m spectrometer. A theoretical rotational CARS model for CO(2) was developed for evaluation of the experimental spectra. The evaluated mean temperatures of the recorded single-shot dual-broadband rotational coherent anti-Stokes Raman spectroscopy (DB-RCARS) spectra using this model showed good agreement with thermocouple temperatures, and the relative standard deviation of evaluated single-shot temperatures was generally 2-3%. Simultaneous thermometry and relative CO(2)/N(2)-concentration measurements were demonstrated in the product gas of premixed laminar CO/air flames at atmospheric pressure. Although the model proved to be accurate for thermometry up to 1143 K, limitations were observed at flame temperatures where temperatures were overestimated and relative CO(2)/N(2) concentrations were underestimated. Potential sources for these discrepancies are discussed.     

Surface-enhanced Raman spectroscopy biosensors: excitation spectroscopy for optimisation of substrates fabricated by nanosphere lithography

In the 28 years since its discovery, surface-enhanced Raman scattering (SERS) has progressed from model system studies of pyridine on a roughened silver electrode to state-of-the-art surface science studies and real-world sensing applications. Each year, the number of SERS publications increases as nanoscale material design techniques advance and the importance of trace analyte detection increases. To achieve the lowest limits of detection, both the relationship between surface nanostructure and laser excitation wavelength and the analyte-surface binding chemistry must be carefully optimised. This work exploits the highly tunable nature of nanoparticle optical properties to establish the optimisation conditions. Two methods are used to study the optimised conditions of the SERS substrate: plasmon-sampled and wavelength-scanned surfaced Raman excitation spectroscopy (SERES). The SERS enhancement condition is optimised when the energy of the localised surface plasmon resonance of the nanostructures lies between the energy of the excitation wavelength and the energy of the vibration band of interest. These optimised conditions enabled the development of SERS-based sensors for the detection of a Bacillus anthracis biomarker and glucose in a serum-protein matrix.     

Fiber-optic probes with improved excitation and collection efficiency for deep-UV Raman and resonance Raman spectroscopy

The ability of ultraviolet resonance Raman spectroscopy (UVRRS) to determine structural, environmental, and analytical information concerning low-concentration aqueous biomolecules makes it a powerful bioanalytical and biophysical technique. Unfortunately, its utility has been limited by experimental requirements that preclude in situ or in vivo studies in most cases. We have developed the first high-performance fiber-optic probes suitable for long-term use in pulsed UVRRS applications in the deep- UV (DUV, 205-250 nm). The probes incorporate recently developed improved ultraviolet (IUV) fibers that do not exhibit the rapid solarization and throughput decay that previously hampered the use of optical fibers for delivering pulsed, DUV light. A novel 90 degrees mirrored collection geometry is used to overcome the inner-filtering effects that plague flush-probe geometries. The IUV fibers are characterized with respect to their efficacy at transmitting pulsed, DUV laser light, and prototype probes are used to obtain pulsed UVRRS data of aromatic amino acids, proteins, and hormones at low concentrations with 205-240-nm pulsed excitation. Efficient probe geometries and fabrication methods are presented. The performance of the probes in examining resonance-enhanced Raman signals from absorbing chromophores is investigated, and the optimal excitation wavelength is shown to be significantly red-shifted from the maximum of the resonance Raman enhancement profile. Generally applicable procedures for determining optimal experimental conditions are also introduced.     

Evaluation of two different gas temperatures and their volumetric fraction from broadband N(2) coherent anti-Stokes Raman spectroscopy spectra

Technical flames often contain regions of high temperature gradients at a length scale that is smaller than or comparable with the size of the probe volume used. In these situations the coherent anti-Stokes Raman spectroscopy (CARS) signal is composed of contributions of gases of different temperatures. Here a fitting routine is presented that allows the evaluation of the different temperatures that occur in the CARS spectra by splitting the temperature mixed spectra into contributions of two main temperatures. Additionally, the volumetric fraction of both gas components with those two different temperatures can be determined. The evaluation procedure has been tested by the use of measured temperature mixed CARS spectra that have been taken in two gas samples with different gas temperatures.     

Time-resolved CO2 thermometry for pressures as great as 5 MPa by use of pure rotational coherent anti-Stokes Raman scattering

Pure rotational coherent anti-Stokes Raman scattering measurements of pure CO2 have been performed in a temperature range from 300 to 773 K and for pressure from 0.1 to 5 MPa for the purpose of time-resolved CO2 thermometry. Particular emphasis was put on the comparison of several line-width approximations to model the experimental spectra. Generally good agreement of the temperature mean values with the thermocouple reference has been found for all models over almost the whole pressure and temperature range investigated. The standard deviations, which increased with temperature, were comparable with or better than the results gained for single-shot measurements of pure N2 or O2-N2 mixtures. Yet for high particle densities close to the critical point of CO2 the limitation of the models became obvious, owing to the strongly increased influence of motional narrowing effects. The characteristics of these effects have been demonstrated by measurements even closer to the critical conditions.     

Near-resonance enhanced O2 detection for dual-broadband pure rotational coherent anti-Stokes Raman scattering with an ultraviolet-visible setup at 266 nm

Broadband and dual-broadband coherent anti-Stokes Raman scattering (CARS) are widely established tools for nonintrusive gas diagnostics. Up to now the investigations have been mainly performed for electronic nonresonant conditions of the gas species of interest. We report on the enhancement of the O2-N2 detection limit of dual-broadband pure rotational CARS by shifting the wavelength of the narrowband pump laser from the commonly used 532-266 nm. This enhancement is caused when the Schumann-Runge absorption band is approached near 176 nm. The principal concept of this experiment, i.e., covering the Raman resonance with a single- or dual-broadband combination of lasers in the visible range and moving only the narrowband probe laser near or directly into electronic resonant conditions in the UV range, should also be applicable to broadband CARS experiments to directly exploit electronic resonance effects for the purpose of single-shot concentration measurements of minority species. To quantify the enhancement in O2 sensitivity, comparative measurements at both a 266 and a 532 nm narrowband pump laser wavelength are presented, employing a 4-dicyanomethylene-2-methyl-6-(p-dimethylaminostyryl)-4H-pyram (DCM) dye laser as a broadband laser source at 635 nm. An increase of approximately equal to 13% in the ratio of the rotational CARS cross sections of O2 and N2 was obtained. The broad spectral width of the CARS excitation profile was approximately equal for both setups. Further enhancement should be achievable by shifting the narrowband pump laser closer toward 176 nm, for example, with a frequency-doubled optical parametric oscillator or an excimer laser. The principal concept of this experiment should also be applicable to broadband CARS experiments to directly exploit electronic resonance effects of the narrowband pump laser with electronic transitions of minority species for the purpose of single-shot concentration measurements of those species.     

Simultaneous temperature and relative nitrogen-oxygen concentration measurements in air with pure rotational coherent anti-Stokes Raman scattering for temperatures to as high as 2050 K

The accuracy of temperature and simultaneous relative N(2) -O(2) concentration measurements of accumulated as well as of single-pulse rotational coherent anti-Stokes Raman spectra has been investigated in air in the temperature range from 300 to 2050 K. The experimental spectra were taken in a high-temperature oven at atmospheric pressure for a constant oxygen concentration of 20.9% (air). The evaluation procedure is based on the energy-corrected sudden-power scaling law. The agreement of the thermocouple readings with the mean values of the evaluated coherent anti-Stokes Raman spectroscopy temperatures is higher than 50 K and independent of the temperature. The evaluated oxygen concentration is found to be in the range from 20.0 to 21.7% and is also independent of the temperature.