Journal of Physical Chemistry, Vol.99, No.39, 14323-14333, 1995
Interaction of HCl with Water Clusters - (H2O)(N)HCl, N=1-3
Ab initio MP2 equilibrium geometries of the clusters (H2O)(m)HCl, m = 1-3, and (H2O)(m), n = 1-4, are reported. It is found that the clusters form hydrogen-bonded rings, with HCl acting as a proton donor. There is a significant increase in the HCl bond length as the cluster size increases, as well as a large red-shift in the HCl stretching frequency. The dissociation energy of HCl from (H2O)(m)HCl is appreciably larger for the trimer and tetramer than for the dimer, which is a consequence of cooperativity effects in the hydrogen bonds. We discuss the relevance of our findings to the understanding of the adsorption of HCl on ice.
Keywords:INFRARED PREDISSOCIATION SPECTRA;DISTRIBUTED MULTIPOLE ANALYSIS;NITRIC-ACID TRIHYDRATE;MATRIX-ISOLATION;VANDERWAALS COMPLEXES;STATIONARY-POINTS;SOLID NITROGEN;ICE SURFACES;BASIS-SETS;GAS-PHASE