Accurate measurements and temperature dependence of the water vapor self-continuum absorption in the 2.1 μm atmospheric window

• Published in: The Journal of chemical physics 2015-10, Vol.143 (13), p.134304-134304
• Main Authors: Ventrillard, I, Romanini, D, Mondelain, D, Campargue, A
• Format: Article
• Language: English
• Subjects: ABSORPTION; ABSORPTION SPECTROSCOPY; Atmospheric windows; Broadband; CLIMATIC CHANGE; CROSS SECTIONS; DIMERS; DISSOCIATION ENERGY; Energy of dissociation; EVALUATION; FOURIER TRANSFORM SPECTROMETERS; FOURIER TRANSFORMATION; Fourier transforms; Free energy; Heat of formation; Infrared windows; INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; Optical feedback; Optics; Physics; SIGNALS; SPECTRA; Spectrum analysis; Temperature; TEMPERATURE DEPENDENCE; Vapor pressure; WATER VAPOR
• ISSN: 0021-9606; 1089-7690
• DOI: 10.1063/1.4931811

In spite of its importance for the evaluation of the Earth radiative budget, thus for climate change, very few measurements of the water vapor continuum are available in the near infrared atmospheric windows especially at temperature conditions relevant for our atmosphere. In addition, as a result of the difficulty to measure weak broadband absorption signals, the few available measurements show large disagreements. We report here accurate measurements of the water vapor self-continuum absorption in the 2.1 μm window by Optical Feedback Cavity Enhanced Absorption Spectroscopy (OF-CEAS) for two spectral points located at the low energy edge and at the center of the 2.1 μm transparency window, at 4302 and 4723 cm(-1), respectively. Self-continuum cross sections, CS, were retrieved with a few % relative uncertainty, from the quadratic dependence of the spectrum base line level measured as a function of water vapor pressure, between 0 and 16 Torr. At 296 K, the CS value at 4302 cm(-1) is found 40% higher than predicted by the MT_CKD V2.5 model, while at 4723 cm(-1), our value is 5 times larger than the MT_CKD value. On the other hand, these OF-CEAS CS values are significantly smaller than recent measurements by Fourier transform spectroscopy at room temperature. The temperature dependence of the self-continuum cross sections was also investigated for temperatures between 296 K and 323 K (23-50 °C). The derived temperature variation is found to be similar to that derived from previous Fourier transform spectrometer (FTS) measurements performed at higher temperatures, between 350 K and 472 K. The whole set of measurements spanning the 296-472 K temperature range follows a simple exponential law in 1/T with a slope close to the dissociation energy of the water dimer, D0 ≈ 1100 cm(-1).