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The weakly-bound molecular clusters (D2O)2-CO and (D2O)3-CO are observed inthe C-O stretch fundamental region (~2150 cm-1), and theirrotationally-resolved infrared spectra yield precise rotational parameters. Thecorresponding H2O clusters are also observed, but their bands are broadened bypredissociation, preventing detailed analysis. The rotational parameters areinsufficient in themselves to determine cluster structures, so ab initiocalculations are employed, and good agreement between the experimental andtheory is found for the most stable cluster isomers, yielding the basic clustergeometries as well as confirming the assignments to (D2O)2-CO and (D2O)3-CO.The trimer, (D2O)2-CO, has a near-planar geometry with one D atom from each D2Oslightly out of the plane. The tetramer, (D2O)3-CO, has the water moleculesarranged in a cyclic quasi-planar ring similar to the water trimer, with thecarbon monoxide located 'above' the ring and roughly parallel to its plane. Thetunneling effects observed in the free water dimer and trimer are quenched bythe presence of CO. The previously observed water-CO dimer together with thetrimer and tetramer reported here represent the first three steps in thesolvation of carbon monoxide.

Micro-solvation of CO in water: Infrared spectra and structural calculations for (D$_2$O)$_2$-CO and (D$_2$O)$_3$-CO