Increase of Radiative Forcing through Midinfrared Absorption by Stable CO₂ Dimers?

We performed matrix-isolation infrared (MI-IR) spectroscopy of carbon dioxide monomers, CO₂, and dimers, (CO₂)₂, trapped in neon and in air. On the basis of vibration configuration interaction (VCI) calculations accounting for mode coupling and anharmonicity, we identify additional infrared-active bands in the MI-IR spectra due to the (CO₂)₂ dimer. These bands are satellite bands next to the established CO₂ monomer bands, which appear in the infrared window of Earth's atmosphere at around 4 and 15 μm. In a systematic carbon dioxide mixing ratio study using neon matrixes, we observe a significant fraction of the dimer at mixing ratios above 300 ppm, with a steep increase up to 1000 ppm. In neon matrix, the dimer increases the IR absorbance by about 15% at 400 ppm compared to the monomer absorbance alone. This suggests a high fraction of the (CO₂)₂ dimer in our matrix experiments. In atmospheric conditions, such increased absorbance would significantly amplify radiative forcings and, thus, the greenhouse warming. To enable a comparison of our laboratory experiment with various atmospheric conditions (Earth, Mars, Venus), we compute the thermodynamics of the dimerization accordingly. The dimerization is favored at low temperatures and/or high carbon dioxide partial pressures. Thus, we argue that matrix isolation does not trap the gas composition "as is". Instead, the gas is precooled to 40 K, where CO₂ dimerizes before being trapped in the matrix, already at very low carbon dioxide partial pressures. In the context of planetary atmospheres, our results improve understanding of the greenhouse effect for planets of rather thick CO₂ atmospheres such as Venus, where a significant fraction of the (CO₂)₂ dimer can be expected. There, the necessity of including the mid-IR absorption by stable (CO₂)₂ dimers in databases used for modeling radiative forcing, such as HITRAN, arises.