Real-time standoff detection of nitrogen isotopes in ammonia plumes using a swept external cavity quantum cascade laser.

A swept-wavelength external cavity quantum cascade laser is used to measure time-resolved NH315 and NH314 concentrations and isotope ratios in a turbulent plume source located at 10 m standoff distance. Measurements show excellent agreement with expected values of isotope ratios for samples with natural and enriched N15 abundance. Detection sensitivity of 150 ppb*m is demonstrated for a 50 ms measurement interval, improving to 10 ppb*m with 10 s averaging, with isotopic precision as good as 0.8%.

Elucidating uranium monoxide spectral features from a laser-produced plasma.

Uranium, because of its pyrophoricity, oxidizes rapidly in an oxygen-containing high-temperature environment. However, so far, the identification of uranium oxide (UO) emission from a laser-produced plasma system is limited to a spectral feature around 593.55 nm. The aim of this study is to elucidate UO emission features in the visible spectral regime from uranium plasmas generated in an environment with varying oxygen concentrations. The plasmas are produced by focusing nanosecond laser pulses on a uranium metal target in a controlled ambient environment. Space- and time-resolved optical emission spectroscopic investigations are used for isolating UO molecular emission structures from crowded U atomic line emission. Our studies highlight that the emission from a U plasma, even in the presence of trace oxygen is accompanied by a strong background-like emission with partially resolved bands from uranium monoxide and higher oxides. We also report several UO spectral emission bands in the visible spectral region.

Dual-comb spectroscopy of laser-induced plasmas.

Dual-comb spectroscopy has become a powerful spectroscopic technique in applications that rely on its broad spectral coverage combined with high frequency resolution capabilities. Experiments to date have primarily focused on detection and analysis of multiple gas species under semi-static conditions, with applications ranging from environmental monitoring of greenhouse gases to high-resolution molecular spectroscopy. Here, we utilize dual-comb spectroscopy to demonstrate broadband, high-resolution, and time-resolved measurements in a laser-induced plasma. As a demonstration, we simultaneously detect trace amounts of Rb and K in solid samples with a single laser ablation shot, with transitions separated by over 6 THz (13 nm) and spectral resolution sufficient to resolve isotopic and ground state hyperfine splittings of the Rb D2 line. This new spectroscopic approach offers the broad spectral coverage found in the powerful techniques of laser-induced breakdown spectroscopy (LIBS) while providing the high-resolution and accuracy of cw laser-based spectroscopies.

Evolution of uranium monoxide in femtosecond laser-induced uranium plasmas.

We report on the observation of uranium monoxide (UO) emission following fs laser ablation (LA) of a uranium metal sample. The formation and evolution of the molecular emission is studied under various ambient air pressures. Observation of UO emission spectra at a rarefied residual air pressure of ~1 Torr indicates that the UO molecule is readily formed in the expanding plasma with trace concentrations of oxygen present within the vacuum chamber. The persistence of the UO emission exceeded that of the atomic emission; however, the molecular emission was delayed in time compared to the atomic emission due to the necessary cooling and expansion of the plasma before the UO molecules can form.

Two-dimensional fluorescence spectroscopy of uranium isotopes in femtosecond laser ablation plumes.

We demonstrate measurement of uranium isotopes in femtosecond laser ablation plumes using two-dimensional fluorescence spectroscopy (2DFS). The high-resolution, tunable CW-laser spectroscopy technique clearly distinguishes atomic absorption from 235U and 238U in natural and highly enriched uranium metal samples. We present analysis of spectral resolution and analytical performance of 2DFS as a function of ambient pressure. Simultaneous measurement using time-resolved absorption spectroscopy provides information on temporal dynamics of the laser ablation plume and saturation behavior of fluorescence signals. The rapid, non-contact measurement is promising for in-field, standoff measurements of uranium enrichment for nuclear safety and security.

Shock Wave Mediated Plume Chemistry for Molecular Formation in Laser Ablation Plasmas.

Although it is relatively straightforward to measure the ionic, atomic, molecular, and particle emission features from laser ablation plumes, the associated kinetic and thermodynamic development leading to molecular and nanocluster formation remain one of the most important topics of analytical chemistry and material science. Very little is known, for instance, about the evolutionary paths of molecular and nanocluster formation and its relation to laser plume hydrodynamics. This is, to a large extent; due to the complexity of numerous physical processes that coexist in a transient laser-plasma system. Here, we report the formation mechanisms of molecules during complex interactions of a laser-produced plasma plume expanding from a high purity aluminum metal target into ambient air. It is found that the plume hydrodynamics plays a great role in redefining the plasma thermodynamics and molecular formation. Early in the plasma expansion, the generated shock wave at the plume edge acts as a barrier for the combustion process and molecular formation is prevalent after the shock wave collapse. The temporally and spatially resolved contour mapping of atoms and molecules in laser ablation plumes highlight the formation routes and persistence of species in the plasma and their relation to plume hydrodynamics.

Characterization of a swept external cavity quantum cascade laser for rapid broadband spectroscopy and sensing.

The performance of a rapidly swept external cavity quantum cascade laser (ECQCL) system combined with an open-path Herriott cell was evaluated for time-resolved measurements of chemical species with broad and narrow absorption spectra. A spectral window spanning 1278 - 1390 cm(-1) was acquired at a 200 Hz acquisition rate, corresponding to a tuning rate of 2x10(4) cm(-1)/s, with a spectral resolution of 0.2 cm(-1). The capability of the ECQCL to measure < 100 ppbv changes in nitrous oxide (N(2)O) and 1,1,1,2-tetrafluoroethane (F134A) concentrations on millisecond timescales was demonstrated in simulated plume studies with releases near the open-path Herriott cell. Absorbance spectra measured using the ECQCL system exhibited noise-equivalent absorption coefficients of 5x10(-9) cm(-1)Hz(-1/2). For a spectrum acquisition time of 5 ms, noise-equivalent concentrations (NEC) for N(2)O and F134A were measured to be 70 and 16 ppbv respectively, which improved to sub-ppbv levels with averaging to 100 s. Noise equivalent column densities of 0.64 and 0.25 ppmv × m in 1 sec are estimated for N(2)O and F134A.

A quantum cascade laser cw cavity ringdown spectrometer coupled to a supersonic expansion source.

A new instrument has been constructed that couples a supersonic expansion source to a continuous wave cavity ringdown spectrometer using a Fabry-Perot quantum cascade laser (QCL). The purpose of the instrument is to enable the acquisition of a cold, rotationally resolved gas phase spectrum of buckminsterfullerene (C(60)). As a first test of the system, high resolution spectra of the nu(8) vibrational band of CH(2)Br(2) have been acquired at approximately 1197 cm(-1). To our knowledge, this is the first time that a vibrational band not previously recorded with rotational resolution has been acquired with a QCL-based ringdown spectrometer. 62 transitions of the three isotopologues of CH(2)Br(2) were assigned and fit to effective Hamiltonians with a standard deviation of 14 MHz, which is smaller than the laser frequency step size. The spectra have a noise equivalent absorption coefficient of 1.4 x 10(-8) cm(-1). Spectral simulations of the band indicate that the supersonic source produces rotationally cold (approximately 7 K) molecules.