Helium Nanodroplet Study of the Hydrogen-Bonded OH Vibrations in HCl-H2O Clusters

Abstract

Mixed (HCl)(N)(H2O)(M) clusters have been assembled in He droplets from the constituting molecules. Spectra of the clusters were obtained in the range of hydrogen-bonded OH vibrations (3100-3700 cm(-1)) by infrared laser depletion spectroscopy. The observed bands were assigned to cyclic hydrogen-bonded aggregates containing up to two HCl and three H2O molecules. The obtained frequencies are in good agreement with the results of harmonic quantum chemical calculations upon appropriate uniform shifts mimicking anharmonic corrections. Although larger clusters containing up to six water molecules were also produced in the droplets, their spectra were found to contribute to the unresolved signal in the range 3250-3550 cm(-1). The fact that no narrow bands could be unambiguously assigned to the mixed clusters containing more than three water molecules may indicate that such clusters exist in many isomeric forms that lead to overlapped and unresolved bands giving rise to broad structureless features. Another possible explanation includes the formation of elusive zwitterionic clusters, whose bands may have considerable breadth due to electrostatic coupling of different vibrational modes and concomitant intramolecular vibrational relaxation.