Far infrared measurements of absorptions by CH4+CO2 and H2+CO2 mixtures and implications for greenhouse warming on early Mars

TL;DR

This study experimentally measures infrared absorption by gas mixtures relevant to early Mars' climate, validating some theoretical predictions and providing new data on collision-induced absorption crucial for understanding planetary atmospheres.

Contribution

It provides new experimental data on collision-induced absorption of H$_2$+CO$_2$ and CH$_4$+CO$_2$ mixtures, confirming some theoretical models and highlighting differences in absorption features.

Findings

H$_2$+CO$_2$ and CH$_4$+CO$_2$ CIAs are stronger than N$_2$ mixtures.

Experimental CIAs differ from previous theoretical predictions.

Line-mixing models describe CO$_2$ line-wing behavior well.

Abstract

We present an experimental study of the absorption, between 40 and 640 cm$^{-1}$, by CO$_2$, CH$_4$ and H$_2$ gases as well as by H$_2$+CO$_2$ and CH$_4$+CO$_2$ mixtures at room temperature. A Fourier transform spectrometer associated to a multi-pass cell, whose optics were adjusted to obtain a 152 m pathlength, were used to record transmission spectra at total pressures up to about 0.98 bar. These measurements provide information concerning the collision-induced absorption (CIA) bands as well as about the wing of the CO$_2$ 15 $\mu$m band. Our results for the CIAs of pure gases are, within uncertainties, in agreement with previous determinations, validating our experimental and data analysis procedures. We then consider the CIAs by H$_2$+CO$_2$ and CH$_4$+CO$_2$ and the low frequency wing of the pure CO$_2$ 15 $\mu$m band, for which there are, to our knowledge, no previous measurements. We confirm experimentally the theoretical prediction of Wordsworth et al. 2017 that the H$_2$+CO$_2$ and CH$_4$+CO$_2$ CIAs are significantly stronger in the 50-550 cm$^{-1}$ region than those of H$_2$+N$_2$ and CH$_4$+N$_2$, respectively. However, we find that the shape and the strength of these recorded CIAs differ from the aforementioned predictions. For the pure CO$_2$ line-wings, we show that both the $\chi$-factor deduced from measurements near 4 $\mu$m and a line-mixing model very well describe the observed strongly sub-Lorentzian behavior in the 500-600 cm$^{-1}$ region. These experimental results open renewed perspectives for studies of the past climate of Mars and extrasolar analogues.