Electronic and mechanical anharmonicities in the vibrational spectra of the H-bonded, cryogenically cooled X- • HOCl (X=Cl, Br, I) complexes: Characterization of the strong anionic H-bond to an acidic OH group

We report vibrational spectra of the H2-tagged, cryogenically cooled X- center dot 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- center dot (H2O)n clusters with HOCl molecules at low pressure (similar to 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 that are similar to those displayed by the X- center dot 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- center dot HOD complexes. Published under an exclusive license by AIP Publishing.

Automated summary

In this study, the vibrational spectra of H2-tagged, cryogenically cooled X- center dot HOCl (X = Cl, Br, and I) ion-molecule complexes were investigated using electronic structure calculations and an anharmonic theoretical treatment. The results showed the presence of additional bands in the band patterns, similar to X- center dot HOD analogs, indicating excitations of nominally IR forbidden overtones and combination bands.