Study of HCl Clusters in Helium Nanodroplets: Experiments and ab Initio Calculations as Stepping Stones from Gas Phase to Bulk

Abstract

Presented here are the results of the joint theoretical and infrared laser spectroscopic study of the hydrogen chloride monomer and clusters, (HCl)n (n=1-6), isolated in helium nanodroplets. The H-Cl stretching bands of the dimers and trimers show a large increase in the band intensity as well as low frequency shift with respect to that in a single HCl molecule. The average frequency of the bands for clusters larger than trimers remains approximately constant, which correlates well with the onset of the folded cyclic structure and the full development of the hydrogen bonding in larger clusters. The structure of the clusters was found to be cyclic planar for trimers, slightly twisted square planar for tetramers, envelope-like for pentamers, and folded pseudobipyramidal for hexamers. This change in structure upon an increase of the cluster size can be seen as an early stage of the structural transition to the HCl solid, which consists of zigzag chains of HCl molecules. Spectra of large clusters of about 500 molecules consist of a single band, which encompasses the same frequency range of trimers through hexamers.