Thirteen specific infrared bands in the 2350 cm−1 region are assigned to carbon dioxide clusters, (CO2)N, with N = 6, 7, 9, 10, 11, 12 and 13. The spectra are observed in direct absorption using a tuneable infrared laser to probe a pulsed supersonic jet expansion of a dilute mixture of CO2 in He carrier gas. Assignments are aided by cluster structure calculations made using two reliable CO2 intermolecular potential functions. For (CO2)6, two highly symmetric isomers are observed, one with S6 symmetry (probably the more stable form), and the other with S4 symmetry. (CO2)13 is also symmetric (S6), but the remaining clusters are asymmetric tops with no symmetry elements. The observed rotational constants tend to be slightly (≈2%) smaller than those from the predicted structures. The bands have increasing vibrational blueshifts with increasing cluster size, similar to those predicted by the resonant dipole-dipole interaction model but significantly larger in magnitude.
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