Spectroscopic studies of CO2 trapped in rare gas matrices

Low temperature (5 K) high resolution (0.15 and 0.03 cm⁻¹) absorption spectra of ¹³CO₂ have been recorded in neon, argon, krypton, and xenon matrices, in the ν₃ and ν₂ regions. Diffusion experiments have been performed in krypton and xenon in order to identify vibrational traps which could be responsible for the decrease and shortening of the emission observed after laser excitation: high-frequency structures in the ν₃ region are assigned to dimers and a doubling of the monomer line is due to a site effect. In neon, only a double substitutional site, with a splitting of the degenerate ν₂ vibration, is observed. In argon, as previously reported, a single and a double site are characterized. In krypton and xenon, where ν₂ is not split, only single sites would be predicted. As one of them exhibits a ν₃ line highly sensitive to temperature, we expect a large coupling with the lattice and a fast vibrational relaxation. This site is very likely the vibrational trap we are looking for.