Fitting of calibration-free scanned-wavelength-modulation spectroscopy spectra for determination of gas properties and absorption lineshapes

The development and initial demonstration of a scanned-wavelength, first-harmonic-normalized, wavelength-modulation spectroscopy with nf detection (scanned-WMS-nf/1f) strategy for calibration-free measurements of gas conditions are presented. In this technique, the nominal wavelength of a modulated tunable diode laser (TDL) is scanned over an absorption transition to measure the corresponding scanned-WMS-nf/1f spectrum. Gas conditions are then inferred from least-squares fitting the simulated scanned-WMS-nf/1f spectrum to the measured scanned-WMS-nf/1f spectrum, in a manner that is analogous to widely used scanned-wavelength direct-absorption techniques. This scanned-WMS-nf/1f technique does not require prior knowledge of the transition linewidth for determination of gas properties. Furthermore, this technique can be used with any higher harmonic (i.e., n>1), modulation depth, and optical depth. Selection of the laser modulation index to maximize both signal strength and sensitivity to spectroscopic parameters (i.e., gas conditions), while mitigating distortion, is described. Last, this technique is demonstrated with two-color measurements in a well-characterized supersonic flow within the Stanford Expansion Tube. In this demonstration, two frequency-multiplexed telecommunication-grade TDLs near 1.4 μm were scanned at 12.5 kHz (i.e., measurement repetition rate of 25 kHz) and modulated at 637.5 and 825 kHz to determine the gas temperature, pressure, H2O mole fraction, velocity, and absorption transition lineshape. Measurements are shown to agree within uncertainty (1%-5%) of expected values.