Laser mass spectrometric analysis of polycyclic aromatic hydrocarbons with wide wavelength range laser multiphoton ionization spectroscopy

In many analytical techniques, 1+1 resonance-enhanced multiphoton ionization (1+1 REMPI) is used because it is an efficient and optically selective soft ionization method. While 1+1 REMPI of jet-cooled molecules has been extensively studied, little has been reported so far about this mechanism as it is used in analytical techniques, that is, in the cases where the molecules are not jet-cooled and where widely varying ionization wavelengths are employed. We used two-step laser mass spectrometry (L2MS) to study the wavelength (238-310 nm) dependence and the laser pulse energy dependence of the ion yield for 17 polycyclic aromatic hydrocarbons (PAHs). We discuss how these data allow prediction of the efficiency of 1+1 REMPI for a given compound. These advances open new perspectives for better understanding the L2MS spectra obtained directly from complex mixtures such as environmental samples.     

Resonance-enhanced multiphoton ionization time-of-flight mass spectrometry for detection of nitrogen containing aliphatic and aromatic compounds: resonance-enhanced multiphoton ionization spectroscopic investigation and on-line analytical application

Resonance-enhanced multiphoton ionization (REMPI) combined with time-of-flight mass spectrometry (TOFMS) is an analytical method capable of on-line monitoring of trace compounds in complex matrices. A necessary prerequisite for substance selective detection is spectroscopic investigation of the target molecules. Several organic nitrogen compounds comprising aliphatic and aromatic amines, nitrogen heterocyclic compounds, and aromatic nitriles are spectroscopically investigated with a tunable narrow bandwidth optical parametric oscillator (OPO) laser system providing a scannable wavelength range between 220 and 340 nm. These species are known as possible precursors in fuel-NO formation from combustion of solid fuels such as biomass and waste. A newly conceived double inlet system was used in this study, which allows rapid change between effusive and supersonic molecular beams. The resulting REMPI spectra of the compounds are discussed with respect to electronic transitions that could be utilized for a selective ionization of these compounds in complex mixtures such as combustion and process gases. The practicability of this approach is demonstrated by wavelength selected on-line REMPI-TOFMS detection of aniline and cyanonaphthalene in the burning chamber of a waste incineration plant. REMPI mass spectra recorded at different excitation wavelengths as well as variations in time show the utilization of species-selective REMPI-TOFMS detection for on-line monitoring of crucial substances in pollutant formation.     

Continuous-wave bistatic laser Doppler wind sensor

A coherent laser radar has been built by use of a master-oscillator power-amplifier arrangement in which the master oscillator is an external-cavity semiconductor laser and the power amplifier is an erbium-doped fiber amplifier with ~1-W output at a wavelength of 1.55 mum. The beams are routed within single-mode optical fiber, allowing modular construction of the optical layout with standard components. The system employs separate transmit and receive optics (a bistatic configuration) and has sufficient sensitivity for reliable Doppler wind-speed detection in moderate scattering conditions at short range (to as much as ~200 m). The bistatic arrangement leads to a well-defined probe volume formed by the intersection of the transmitted laser beam with the virtual backpropagated local-oscillator beam. This could be advantageous for applications in which the precise localization of wind speed is required (e.g., wind tunnel studies) or in which smoke, low cloud, or solid objects can lead to spurious signals. The confinement of the probe volume also leads to a reduction in the signal power. A theoretical study has been carried out on the reduction in wind signal strength compared with the monostatic arrangement, and the results are compared with experimental observation.     

Experiments concerning resonance-enhanced multiphoton ionization probe measurements of flame-species profiles

Resonance-enhanced multiphoton ionization (REMPI) detection of radical species in low-pressure laboratory flames is a promising tool for the development and refinement of combustion models. For accurate REMPI species concentration measurements in flame zones with inherently high background ionization levels, an understanding of the influence of plasma sheaths on REMPI probe response is required. Proper probe response is found to depend on careful control of probe-biasing and laserfocusing conditions. Only negatively biased probes are suitable, because of the influences of secondary ionization on the response of positively biased probes. In situ probe calibration procedures with the (2 + 2) REMPI of N(2) at 270.6 nm are described. Detection of O atoms in a stoichiometric 20-Torr methane-oxygen flame permits a precise comparison of both laser-induced fluorescence and REMPI measurements with flame-modeling results.     

Isotope-selective excitation of 41Ca isotope in Doppler-free two-photon continuous-wave excitation: a case study

Seven schemes are studied theoretically for Doppler-free two-photon excitation of rare (41)Ca isotope using single-mode continuous-wave lasers. The ionization efficiencies and optical selectivities for all the schemes are calculated for various powers of the excitation and ionization lasers and for various focusing conditions of the two lasers. To maximize the ionization efficiencies and the optical selectivities, wavelength-dependent Stark compensation is used. Certain laser wavelengths of the ionization step termed as magic wavelengths are identified for compensating the Stark shift induced by the excitation laser. The effects of the Stark-shift-induced asymmetry and its reversal by selecting the appropriate magic wavelength for the ionization step for various excitation and ionization laser intensities are investigated. The ionization efficiency and optical selectivity for the best scheme after Stark compensation are found to be 8.4 x 10(-4) and approximately 9 x 10(3), respectively.     

光纤探针型近场光镊光强分布特性的数值模拟

光纤探针型近场光镊是近场光学领域中的新型技术,因其可对纳米尺度微粒直接进行捕获和操纵而受到广泛关注,其光纤探针尖端的近场分布特性影响着纳米粒子捕获及操纵的成败探针金属膜外侧电磁场由光波在针尖小孔处衍射而成,根据夫朗和费衍射公式分析了圆形纳米小孔的光波衍射图样,运用时域有限差分法（FDTD）研究了均匀平面波垂直入射于镀膜光纤探针的近场分布,比较了不同锥角、不同出射孔径、不同金属膜厚度及不同入射波长的近场分布情况,并对不同情况下的通光效率进行了分析。通过对各参数的计算与比较,结果表明,当锥角越大、孔径越大、镀合适膜厚并且入射波长越小时,探针尖端的出射光强越大并具有较大的通光效率     

Resonance-enhanced multiphoton ionization for real-time monitoring of trichloroethylene formed by degradation of tetrachloroethylene using zero-valent zinc

Resonance-enhanced multiphoton ionization (REMPI) is investigated as a potential technique for real-time monitoring of selected volatile organochloride compounds (VOCs). In a proof-of-concept experiment, the progress of the reductive-degradation of tetrachloroethylene (PCE) to trichloroethylene (TCE) by zero-valent zinc was monitored by REMPI measurements performed in the headspace above the PCE solution. Two-photon resonant REMPI spectra of TCE and PCE were recorded over the wavelength range 305-320 nm. The concentrations of PCE and TCE in the headspace were monitored by measurement of the ionization signal with 315.64- and 310.48-nm excitation for PCE and TCE, respectively. Calibration curves yielded a linear range of more than 2 orders of magnitude for both compounds. The REMPI headspace results agreed well with the solution-phase results from gas chromatography analysis, which was used for independent verification of the progress of the reaction.     

Investigation of the Static and Dynamic Characteristics for a Wafer-Fused C-band VCSEL in the Mode of the Optical-Electric Converter

The results of an experimental study for a long wavelength vertical cavity surface-emitting laser of a wafer-fused construction as an effective resonant cavity enhanced photodetector of analog optical signals are described. The device is of interest for a number of promising microwave photonics applications and for creation of a low-cost photoreceiver in a high-speed fiber optics telecommunication system with dense wavelength division multiplexing. The schematic of the testbed, the original technique allowing to calculate the passband of the built-in optical cavity, and the results of measuring dark current, current responsivity, amplitude- and phase-frequency characteristics during the process of photo-detection are demonstrated.     

Simultaneous measurement of nitric oxide (NO) and nitrogen dioxide (NO2) in simulated automobile exhaust using medium pressure ionization-mass spectrometry

In previous papers we have demonstrated two different, two-color resonance-enhanced multiphoton ionization (REMPI) schemes for the simultaneous measurement of trace amounts (ppbV to pptV) of nitrogen monoxide (NO) and nitrogen dioxide (NO(2)). The goal of this study is to provide a laser ionization-mass spectrometric scheme capable of measuring ppmV to ppthV concentrations of NO and NO(2) within vehicle exhaust containing up to ppthV of aromatic hydrocarbons and a time frame of seconds. Two ionization schemes are used here to measure NO and NO(2) in simulated automobile exhaust with three different sources. REMPI Scheme 1 uses broad-bandwidth light and an effusive source to measure NO (limit of detection (LOD) 300 ppmV), NO(2) (LOD 100 ppmV), and aromatic hydrocarbons (via photoionization) along with fragments (via electron impact). REMPI Scheme 2 uses narrow-bandwidth light and a medium pressure laser ionization (MPLI) source to measure NO (LOD 60 ppmV), NO(2) (LOD 3 ppmV), and fragments (via electron impact). The LOD is determined using 10-second sampling times. A newly developed delayed-ion extraction technique for MPLI is then applied to REMPI Scheme 2, dramatically reducing the electron impact signal, so that only NO and NO(2) are observed. We conclude that Scheme 2 with delayed-electron extraction is best suited for measuring in situ NO and NO(2) within engine exhaust.     

A new optical wavelength ratio measurement apparatus: the fringecounting sigmameter

A new, compact and achromatic Michelson-type interferometer with a variable path difference is presented. This “fringe-counting” sigmameter allows measurement of optical wavelength ratios between a laser of unknown wavelength and a reference laser of known wavelength. This apparatus, maintained in a vacuum, measures interference order variations in two stages: integer counting of around 400000 and fractional counting (also called “excess fraction”) with an uncertainty of 10^-3. From these measurements, this “sigmameter” can determine laser wavelength from 0.36 μm to 1.5 μm with an accuracy of 1.10^-8 using a reference stabilized He-Ne laser     

Design and characterization of a high-power laser-induced acoustic desorption probe coupled with a fourier transform ion cyclotron resonance mass spectrometer

We report here the construction and characterization of a high-power laser-induced acoustic desorption (LIAD) probe designed for Fourier transform ion cyclotron resonance mass spectrometers to facilitate analysis of nonvolatile, thermally labile compounds. This "next generation" LIAD probe offers significant improvements in sensitivity and desorption efficiency for analytes with larger molecular weights via the use of higher laser irradiances. Unlike the previous probes which utilized a power-limiting optical fiber to transmit the laser pulses through the probe, this probe employs a set of mirrors and a focusing lens. At the end of the probe, the energy from the laser pulses propagates through a thin metal foil as an acoustic wave, resulting in desorption of neutral molecules from the opposite side of the foil. Following desorption, the molecules can be ionized by electron impact or chemical ionization. Almost an order of magnitude greater power density (up to 5.0x10(9) W/cm2) is achievable on the backside of the foil with the high-power LIAD probe compared to the earlier LIAD probes (maximum power density approximately 9.0x10(8) W/cm2). The use of higher laser irradiances is demonstrated not to cause fragmentation of the analyte. The use of higher laser irradiances increases sensitivity since it results in the evaporation of a greater number of molecules per laser pulse. Measurement of the average velocities of LIAD-evaporated molecules demonstrates that higher laser irradiances do not correlate with higher velocities of the gaseous analyte molecules.     

Analysis of Carbendazim in Agricultural Samples by Laser Desorption and REMPI Time-of-Flight Mass Spectrometry

A method has been developed for the analysis of carbendazim in agricultural samples. This has been accomplished by the combination of laser desorption with resonance-enhanced multi-photon ionization (REMPI) coupled to time-of-flight mass spectrometry detection. After the optimization of the experimental conditions and the location of the resonant wavelength of the substance, several samples of pepper extract enriched with carbendazim were analyzed, finding a detection limit of the same order of magnitude as that of current GC and HPLC techniques, but with higher sensitivity and faster sample preparation.     

Characteristics of calculus fragmentation with Er:YAG laser light emitted by an infrared hollow optical fiber with various sealing caps

We have experimentally quantified calculus fragmentation by Er:YAG laser light. Er:YAG laser light was delivered to an underwater target through a sealed hollow optical fiber. Fragmentation efficiency was obtained for an alumina ball used as a calculus model when sealing caps with various focusing effects were used. Three types of human calculus were analyzed, and their absorption properties at the wavelength of Er:YAG laser light were obtained. The relationships among the absorption properties, calculus constituents, and fragmentation efficiency are discussed.     

Hybrid Wavelength-Time-Domain Interrogation System for Multiplexed Fiber Bragg Sensors Using a Strain-Tuned Erbium-Doped Fiber Laser

A system for the interrogation of fiber Bragg grating (FBG) sensors using a strain-tuned EDF laser with linear cavity is described. An optical switch is spliced to one end of the laser cavity and connects one of two high-strength draw-tower fiber Bragg gratings (DTGs). The gratings are simultaneously tuned by a stretching device and act as the end reflector of the laser cavity. By applying a ramp signal to the actuator synchronized to the optical switch, the laser signal sweeps over two different wavelength intervals, depending on the connected DTG. This approach represents a hybrid wavelength-time-domain interrogation for multiplexed sensors and doubles the number of sensors that may be addressed when compared with single DTG scanning. In addition, the use of the DTG allows a fivefold increase in the strain tuned wavelength interval over standard fiber Bragg gratings. An example application is demonstrated where temperature inside an electrical motor is measured during operation.     

Thermal lens micro optical systems

This paper describes two types of miniaturized thermal lens optical systems that use optical fibers, SELFOC microlenses and light sources. The first system consists of a compact diode pumped solid-state laser (532 nm) as an excitation light source, a laser diode (635 nm) as a probe light source, an acoustoptic modulator as an excitation light modulator, fiber-based and conventional optics, and a detection system that combines a pinhole, an interference filter, and a photodiode. The second system consists of two laser diodes as the excitation (658 nm) and probe (780 nm) light sources, fiber-based optics, and the same detection system as the first one. The performance of the two systems was evaluated by the limit of detection (LOD) using standard solutions of sunset yellow (SY) and nickel(II) phthalocyaninetetrasulfonic acid tetrasodium salt (NiP). The LODs of the first system for SY and second system for NiP were calculated to be 3.7 x 10(-8) (1.7 x 10(-6) AU) and 7.7 x 10(-9) M (3.4 x10(-6) AU), respectively. These results were consistent with the expected values obtained from photothermal parameters.     

Two-photon resonance-enhanced refractive-index change and self-focusing in a dye-solution-filled hollow fiber system

The general behavior of two-photon absorption-enhanced refractive-index change in a third-order nonlinear optical medium is briefly described. The nonlinear medium was the solution of a new dye, trans-4-[p-(N-hydroxyethyl-N-methylamino)styryl]-N-methyl pyridinium iodide (ASPI) in dimethyl sulfoxide as the solvent, that was poured into a 20-cm-long quartz hollow fiber of 100-mum internal diameter. This dye solution has a strong two-photon absorption and subsequent upconversion fluorescence emission when excited with 1064-nm laser radiation. When the input peak intensity reached 500-1500-MW/cm(2) levels, obvious changes in beam profiles of the output IR laser beam were observed due to a self-focusing or self-trapping process occurring inside the fiber system. As a result of this process, highly directional frequency-upconverted superradiant lasing output was obtained with a beam size ~5 times smaller than that of a linearly transmitted He-Ne probe laser beam. The demonstrated mechanism can be useful for fiber laser-amplifier and fiber-integrated optics devices.     

Laser Ultrasonics: Simultaneous Generation by Means of Thermoelastic Expansion and Material Ablation

This paper describes a laser ultrasonic probe capable of generating ultrasound by both thermoelastic expansion and material ablation mechanisms simultaneously. Because bulk wave propagation is centered around a 67° line of sight for thermoelastically generated signals, and near normal (0°) for signals generated by means of ablation, the simultaneous generation by both mechanisms results in a wider range of useful observation angles. The system described uses a Nd:Yag laser with fiber optic delivery and a focusing objective, with an independent receiver, such as an EMAT, interferometer or contact transducer. The optical fiber delivery system allows the probe to be easily positioned (i.e. using a robot), and has the added benefit of allowing a single laser to service several test sites. The focusing objective provides the means for generating ultrasound by either thermoelastic expansion or ablation, or a combination of the two mechanism. The objective also serves to protect the fiber from ablated material and manufacturing contaminants (dust, welding gas, etc.). The resulting system is both physically robust and highly adaptable for a wide range of industrial ultrasonic inspection applications.     

Expanding the realm of fiber optic confocal sensing for probing position, displacement, and velocity

We describe a fiber optic confocal sensor (FOCOS) system that uses an optical fiber and a lens to accurately detect the position of an object at, or close to, the image plane of the fiber tip. The fiber characteristics (diameter and numerical aperture) and optics (lens F/# and magnification) define the span and precision of the sensor and may be chosen to fit a desired application of position and displacement sensing. Multiple measurement points (i.e., fiber-tip images) may be achieved by use of multiple wavelengths in the fiber, so that each wavelength images the fiber at a different plane due to the chromatic dispersion of the optics. Further multiplexing may be achieved by adding fibers on the optical axis. A FOCOS with multiplexed fibers and wavelengths may also be used for velocity measurements.     

Design and experimental characterization of a high-resolution instrument for measuring the extreme-UV absorption of laser plasmas

The performances of a spectrometer for the observation of laser plasma absorption with high spectral and spatial resolution are described. Aspherical optics are used to correct the astigmatism in an extended spectral region. In this way only a small portion of the absorbing medium is probed, thus giving a good selection of the ionization stage acting as the absorption. Moreover, in the focal plane the plasma emission from the absorbing medium is spatially separated from the probe beam, with a consequent enhancement of the measurement sensitivity. The predicted optical performances from a ray tracing are compared with experimental observations for both spectral and spatial resolution.