Effects of Zero-Point Delocalization on the Vibrational Frequencies of Mixed HCl and Water Clusters

We demonstrate the significant effect that large-amplitude zero-point vibrational motion can have on the high-frequency fundamental vibrations of molecular clusters, specifically small (HCl)(n)-(H2O)(m) clusters. Calculations were conducted on a many-body potential, constructed from a mix of new and previously reported semiempirical and high-level ab initio potentials. Diffusion Monte Carlo simulations were performed to determine ground-state wave functions. Visualization of these wave functions indicates that the clusters exhibit delocalized ground states spanning multiple stationary point geometries. The ground states are best characterized by planar ring configurations, despite the clusters taking nonplanar configurations at their global minima. Vibrational calculations were performed at the global minima and the Diffusion Monte Carlo predicted configurations and also using an approach that spans multiple stationary points along a rectilinear normal-mode reaction path. Significantly better agreement was observed between the calculated vibrational frequencies and experimental peak positions when the delocalized ground state was accounted for.