Non-intrusive, in situ detection of ammonia in hot gas flows with mid-infrared degenerate four-wave mixing at 2.3μm

We demonstrate non-intrusive, in situ detection of ammonia (NH3) in reactive hot gas flows at atmospheric pressure using mid-infrared degenerate four-wave mixing (IR-DFWM). IR-DFWM excitation scans were performed in the v2+v3 and v1+v2 vibrational bands of NH3 around 2.3μm for gas flow temperatures of 296, 550 and 820K. Simulations based on spectroscopic parameters from the HITRAN database have been compared with the measurements in order to identify the spectral lines, and an absorption spectrum at 296K has also been measured to compare with the IR-DFWM spectra. The signal-to-noise ratio of the IR-DFWM measurement was found to be higher than that of the absorption measurement. Some spectral lines in the measured IR-DFWM and absorption spectra had no matching lines in the HITRAN simulation. The detection limit of NH3 diluted in N2 with IR-DFWM in this spectral range was estimated at 296, 550 and 820K to be 1.36, 4.87 and 7.06×1016molecules/cm3. The dependence of the NH3 IR-DFWM signal on the quenching properties of the buffer gas flow was investigated by comparing the signals for gas flows of N2, Ar and CO2 with small admixtures of NH3. It was found that the signal dependence on buffer gas was large at room temperature but decreased at elevated temperatures. These results show the potential of IR-DFWM for detection of NH3 in combustion environments

Investigation and compensation of the nonlinear response in photomultiplier tubes for quantitative single-shot measurements.

A concept for time-sensitive optical detectors is described that shows how to confirm whether the detection device is operating in the linear response regime. By evaluating the recorded time decay of a thermographic phosphor, even weak saturation effects far from obvious situations can be identified and further related to either optical or electrical saturation. The concept has been validated by running a PMT detector close to saturation and exposing it to the optical signal decay of two different thermographic phosphors, La(2)O(2)S:Eu and CdWO(4). It was confirmed that short but intense light exposures at the beginning of an individual time decay influence the detector response for the rest of the decaying signal including temporal areas, where the anode current has dropped well below the manufacturer specified current limit. Such situations are common when applying, e.g., phosphor thermometry where it is necessary to retrieve the full decay curve from a single-shot event, i.e., standard techniques based on single-photon counting are omitted. Finally, means of compensation are introduced in order to facilitate the retrieval of useful information from the measurement data when operation in the non-linear response regime is inevitable

Vapor phase tri-methyl-indium seeding system suitable for high temperature spectroscopy and thermometry.

Tri-methyl-indium (TMI) is used as an indium transport molecule to introduce indium atoms to reactive hot gas flows/combustion environments for spectroscopic diagnostics. A seeding system was constructed to allow the addition of an inert TMI laden carrier gas into an air/fuel mixture burning consequently on a burner. The amount of the seeded TMI in the carrier gas can be readily varied by controlling the vapor pressure through the temperature of the container. The seeding process was calibrated using the fluorescent emission intensity from the indium 6(2)S1/2 → 5(2)P1/2 and 6(2)S1/2 → 5(2)P3/2 transitions as a function of the calculated TMI seeding concentration over a range of 2-45 ppm. The response was found to be linear over the range 3-22.5 ppm; at concentrations above 25 ppm there is a loss of linearity attributable to self-absorption or loss of saturation of TMI vapor pressure in the carrier gas flow. When TMI was introduced into a post-combustion environment via an inert carrier gas, molecular transition from InH and InOH radicals were observed in the flame emission spectrum. Combined laser-induced fluorescence and absorption spectroscopy were applied to detect indium atoms in the TMI seeded flame and the measured atomic indium concentration was found to be at the ppm level. This method of seeding organometallic vapor like TMI to a reactive gas flow demonstrates the feasibility for quantitative spectroscopic investigations that may be applicable in various fields, e.g., chemical vapor deposition applications or temperature measurement in flames with two-line atomic fluorescence

Surface Core Level Shifts of Clean and Oxygen Covered Ru(0001)

We have performed high resolution XPS experiments of the Ru(0001) surface, both clean and covered with well-defined amounts of oxygen up to 1 ML coverage. For the clean surface we detected two distinct components in the Ru 3d_{5/2} core level spectra, for which a definite assignment was made using the high resolution Angle-Scan Photoelectron Diffraction approach. For the p(2x2), p(2x1), (2x2)-3O and (1x1)-O oxygen structures we found Ru 3d_{5/2} core level peaks which are shifted up to 1 eV to higher binding energies. Very good agreement with density functional theory calculations of these Surface Core Level Shifts (SCLS) is reported. The overriding parameter for the resulting Ru SCLSs turns out to be the number of directly coordinated O atoms. Since the calculations permit the separation of initial and final state effects, our results give valuable information for the understanding of bonding and screening at the surface, otherwise not accessible in the measurement of the core level energies alone.Comment: 16 pages including 10 figures. Submitted to Phys. Rev. B. Related publications can be found at http://www.fhi-berlin.mpg.de/th/paper.htm

Crystallographic structure of ultrathin Fe films on Cu(100)

We report bcc-like crystal structures in 2-4 ML Fe films grown on fcc Cu(100) using scanning tunneling microscopy. The local bcc structure provides a straightforward explanation for their frequently reported outstanding magnetic properties, i.e., ferromagnetic ordering in all layers with a Curie temperature above 300 K. The non-pseudomorphic structure, which becomes pseudomorphic above 4 ML film thickness is unexpected in terms of conventional rules of thin film growth and stresses the importance of finite thickness effects in ferromagnetic ultrathin films.Comment: 4 pages, 3 figures, RevTeX/LaTeX2.0