In the presence of a halide ion, hypohalous acids can adopt two binding motifs upon formation of the ion-molecule complexes [XHOY] (X, Y = Cl, Br, I): a hydrogen (HB) bond to the acid OH group and a halogen (XB) bond between the anion and the acid halogen. Here we isolate the X-bonded Cl·IOH ion-molecule complex by collisions of I·(HO) clusters with HOCl vapor and measure its vibrational spectrum by IR photodissociation of the H-tagged complex. Anharmonic analysis of its vibrational band pattern reveals that formation of the XB complex results in dramatic lowering of the HOI bending fundamental frequency and elongation of the O-I bond (by 168 cm and 0.13 Å, respectively, relative to isolated HOI). The frequency of the O-I stretch (estimated 436 cm) is also encoded in the spectrum by the weak = 0 → 2 overtone transition at 872 cm.

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http://dx.doi.org/10.1021/acs.jpclett.2c00218DOI Listing

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