The high resolution absorption spectrum of methane in the 10 800-14 000 cm-1 region: literature review, new results and perspectives.

The recent development of high resolution spectrographs for exoplanetary research in the visible range makes suitable an improvement of our knowledge of the high resolution spectrum of methane. In this contribution, the weak and highly congested absorption spectrum of methane in the 10 800-14 000 cm-1 region (0.71-0.93 µm) is considered on the basis of (i) an exhaustive review of the literature over the lasts decades, (ii) the analysis of a spectrum recorded at Kitt Peak by Fourier transform spectroscopy at room temperature, (iii) a very high sensitivity spectrum recorded by cavity ring down spectroscopy near 760 nm. The line list retrieved from the Kitt Peak spectrum includes 12 800 lines between 10 802 and 13 922 cm-1. Together with the CRDS line list in the 13 060-13 300 cm-1 interval (about 2650 lines), the reported FTS dataset represents the first high resolution extensive intensity measurements of methane for wavenumbers above 11 502 cm-1. A very good agreement between our Kitt Peak line list and HITRAN list is found in the 10 800-11 502 cm-1 interval. The "quasi-continuum" absorption background underlying the congested spectrum around 11 200 cm-1 is quantitatively evaluated to about 42% of the absorption by CH4 lines. Previous laser-based investigations are critically reviewed by comparison to the FTS and CRDS experimental data retrieved in the present work. The review of the studies of the minor isotopologues (13CH4, CH3D, CH2D2, and CHD3) is also presented. Intensity comparison with band models used for planetary applications is discussed and confirms the importance of the "quasi-continuum" absorption in the methane spectrum at room temperature. The comparison to the TheoReTs line list obtained by ab initio calculations gives valuable hints for future assignments but the TheoReTS line positions are not sufficiently accurate for application to high resolution exoplanetary spectra in the region. From the various comparisons and results obtained in this work, we conclude that the high frequency absorption spectrum of methane deserves to be revisited by modern cavity-enhanced absorption techniques to fulfil needs both for future analysis of high resolution exoplanetary spectra and for theoretical analysis.

CRDS with a VECSEL for broad-band high sensitivity spectroscopy in the 2.3 µm window.

The integration of an industry ready packaged Sb-based Vertical-External-Cavity Surface-Emitting-Laser (VECSEL) into a Cavity Ring Down Spectrometer (CRDS) is presented. The instrument operates in the important 2.3 µm atmospheric transparency window and provides a high sensitivity (minimum detectable absorption of 9 × 10(-11) cm(-1)) over a wide spectra range. The VECSEL performances combine a large continuous tunability over 120 cm(-1) around 4300 cm(-1) together with a powerful (∼5 mW) TEM00 diffraction limited beam and linewidth at MHz level (for 1 ms of integration time). The achieved performances are illustrated by high sensitivity recordings of the very weak absorption spectrum of water vapor in the region. The developed method gives potential access to the 2-2.7 µm range for CRDS.

The self- and foreign-absorption continua of water vapor by cavity ring-down spectroscopy near 2.35 µm.

The room temperature self- and foreign-continua of water vapor have been measured near 4250 cm(-1) with a newly developed high sensitivity cavity ring down spectrometer (CRDS). The typical sensitivity of the recordings is αmin≈ 6 × 10(-10) cm(-1) which is two orders of magnitude better than previous Fourier transform spectroscopy (FTS) measurements in the spectral region. The investigated spectral interval is located in the low energy range of the important 2.1 µm atmospheric transparency window. Self-continuum cross-sections, CS, were retrieved from the quadratic dependence of the spectrum base line level measured for different water vapor pressures between 0 and 15 Torr, after subtraction of the local water monomer lines contribution calculated using HITRAN2012 line parameters. The CS values were determined with 5% accuracy for four spectral points between 4249.2 and 4257.3 cm(-1). Their values of about 3.2 × 10(-23) cm(2) molecule(-1) atm(-1) are found 20% higher than predicted by the MT_CKD V2.5 model but two times weaker than reported in the literature using FTS. The foreign-continuum was evaluated by injecting various amounts of synthetic air in the CRDS cell while keeping the initial water vapor partial pressure constant. The foreign-continuum cross-section, CF, was retrieved from a linear fit of the spectrum base line level versus the air pressure. The obtained CF values are larger by a factor of 4.5 compared to the MT_CKD values and smaller by a factor of 1.7 compared to previous FTS values. As a result, for an atmosphere at room temperature with 60% relative humidity, the foreign-continuum contribution to the water continuum near 4250 cm(-1) is found to be on the same order as the self-continuum contribution.