Mid-infrared laser spectroscopic determination of isotope ratios of N2O at trace levels using wavelength modulation and balanced path length detection

We present a new mid-infrared laser spectrometer for high-precision measurements of isotopic ratios of molecules at ppm concentrations. Results are discussed for nitrous oxide (N2O), where a precision of 3‰ for a single measurement and a reproducibility of 6‰ have been achieved for a concentration of 825ppm. The room-temperature laser source employed is based on difference-frequency generation delivering a continuous-wave power up to 23μW at wavelengths between 4.3μm and 4.7μm and a line width of 1MHz. Two different measurement methods are compared; wavelength modulation with first-harmonic detection and direct absorption spectroscopy by recording the spectrum with a data-acquisition card. Two different detection schemes were employed; either all isotopomers were measured using the long path (36m) of the multipass cell or a balanced path length detection scheme was used, where the main isotope was measured with a beam along a shorter path (40cm) in the multipass cell. A single-pass reference cell was designed, offering two different path lengths for balanced path length detection. All combinations of measurement methods and detection schemes were tested regarding precision of a single measurement and long-term stability. The advantages and disadvantages of various measurement approaches are discusse

Near-infrared laser based cavity ringdown spectroscopy for applications in petrochemical industry

A simple, economic diode laser based cavity ringdown system for trace-gas applications in the petrochemical industry is presented. As acetylene (C2H2) is sometimes present as an interfering contaminant in the gas flow of ethylene (ethene, C2H4) in a polyethylene production process, an on-line monitoring of such traces is essential. We investigated C2H2-C2H4 mixtures in a gas-flow configuration in real time. The experimental setup consists of a near-infrared external cavity diode laser with an output power of a few mW, standard telecommunication fibers and a home-made gas cell providing a user-friendly cavity alignment. A noise-equivalent detection sensitivity of 4.5×10-8cm-1 Hz-1/2 was achieved, corresponding to a detection limit of 20ppbV C2H2 in synthetic air at 100mbar. In an actual C2H2-C2H4 gas-flow measurement the minimum detectable concentration of C2H2 added to the C2H4 gas stream (which may already contain an unknown C2H2 contamination) increased to 160ppbV. Moreover, stepwise C2H2 concentration increments of 500ppbV were resolved with a 1-min time resolution and an excellent linear relationship between the absorption coefficient and the concentration was foun

The potential of mid-infrared photoacoustic spectroscopy for the detection of various doping agents used by athletes

The feasibility of laser-photoacoustic measurements for the detection and the analysis of different isolated doping agents in the vapour phase is discussed. To the best of our knowledge, this is the first time that photoacoustic vapour-phase measurements of doping substances have been presented. Spectra of different doping classes (stimulants, anabolica, diuretica, and beta blockers) are shown and discussed in terms of their detection sensitivity and selectivity. The potential of laser spectroscopy for detecting the intake of prohibited substances by athletes is explore

Investigation and optimisation of a multipass resonant photoacoustic cell at high absorption levels

A theoretical and experimental investigation of photoacoustic (PA) signals in a resonant multipass PA cell with high background absorption (up to 29m-1) is presented. An analogous electric transmission line model including discontinuity inductances at cross section changes was used to model the first longitudinal acoustic mode of the multipass PA cell equipped with two buffer volumes. This model was validated with experimentally obtained results and used to predict the behaviour of the PA cell for different multipass arrangements and different buffer volume diameters. The highest PA signal is obtained for high pass number and large buffer radius. Increasing the absorption coefficient of the medium enhances the PA signal until a maximum is reached, leading to a minimum for the PA signal sensitivity. For a given background absorption, the number of passes required to maximise the sensitivity depends on the absorption coefficient. The model allows the determination of the best-suited number of passes for a given absorption coefficient and cell geometr

Trace gas monitoring with infrared laser-based detection schemes

The success of laser-based trace gas sensing techniques crucially depends on the availability and performance of tunable laser sources combined with appropriate detection schemes. Besides near-infrared diode lasers, continuously tunable midinfrared quantum cascade lasers and nonlinear optical laser sources are preferentially employed today. Detection schemes are based on sensitive absorption measurements and comprise direct absorption in multi-pass cells as well as photoacoustic and cavity ringdown techniques in various configurations. We illustrate the performance of several systems implemented in our laboratory. These include time-resolved multicomponent traffic emission measurements with a mobile CO2-laser photoacoustic system, a diode-laser based cavity ringdown device for measurements of impurities in industrial process control, isotope ratio measurements with a difference frequency (DFG) laser source combined with balanced path length detection, detection of methylamines for breath analysis with both a near-IR diode laser and a DFG source, and finally, acetone measurements with a heatable multipass cell intended for vapor phase studies on doping agents in urine sample

Thermodynamics of the half-filled Kondo lattice model around the atomic limit

We present a perturbation theory for studying thermodynamic properties of the Kondo spin liquid phase of the half-filled Kondo lattice model. The grand partition function is derived to calculate chemical potential, spin and charge susceptibilities and specific heat. The treatment is applicable to the model with strong couplings in any dimensions (one, two and three dimensions). The chemical potential equals zero at any temperatures, satisfying the requirement of the particle-hole symmetry. Thermally activated behaviors of the spin(charge) susceptibility due to the spin(quasiparticle) gap can be seen and the two-peak structure of the specific heat is obtained. The same treatment to the periodic Anderson model around atomic limit is also briefly discussed.Comment: 5 pages, 3 figures, to appear in Phys. Rev.