Observing the Completion of the First Solvation Shell of Carbon Dioxide in Argon from Rotationally Resolved Spectra

Widespread interest in weakly bound molecular clusters of medium size (5-50 molecules) is motivated by their complicated energy landscapes, which lead to hundreds or thousands of distinct isomers. But most studies are theoretical in nature, and there are no experimental results which provide definitive structural information on completion of the first solvation shell. Here we assign rotationally resolved mid-infrared spectra to argon clusters containing a single carbon dioxide molecule, CO₂-Ar₁₅ and CO₂-Ar₁₇. These mark the completion of the first solvation shell for CO₂ in argon. The assignments are confirmed by nuclear spin intensity alternation in the spectra, a marker of highly symmetric structures for these clusters. Precise values are determined for rotational parameters and for shifts of the CO₂ vibrational frequency induced by the argon atoms. The spectra indicate possible low-frequency (∼2 cm^-1) vibrational modes in these clusters, posing a challenge for future cluster theory.