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  1. We report vibrational spectra of the H 2 -tagged, cryogenically cooled X −  · HOCl (X = Cl, Br, and I) ion–molecule complexes and analyze the resulting band patterns with electronic structure calculations and an anharmonic theoretical treatment of nuclear motions on extended potential energy surfaces. The complexes are formed by “ligand exchange” reactions of X −  · (H 2 O) n clusters with HOCl molecules at low pressure (∼10 −2  mbar) in a radio frequency ion guide. The spectra generally feature many bands in addition to the fundamentals expected at the double harmonic level. These “extra bands” appear in patterns thatmore »are similar to those displayed by the X −  · HOD analogs, where they are assigned to excitations of nominally IR forbidden overtones and combination bands. The interactions driving these features include mechanical and electronic anharmonicities. Particularly intense bands are observed for the v = 0 → 2 transitions of the out-of-plane bending soft modes of the HOCl molecule relative to the ions. These involve displacements that act to break the strong H-bond to the ion, which give rise to large quadratic dependences of the electric dipoles (electronic anharmonicities) that drive the transition moments for the overtone bands. On the other hand, overtone bands arising from the intramolecular OH bending modes of HOCl are traced to mechanical anharmonic coupling with the v = 1 level of the OH stretch (Fermi resonances). These interactions are similar in strength to those reported earlier for the X −  · HOD complexes.« less
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