Born-Oppenheimer molecular dynamics of the hydration of Na+ in a water cluster.

The hydration of Na(+) in a water cluster is studied through all-electron Born-Oppenheimer molecular dynamics. The structure, dipole moment, and vibrational spectrum of the sodium cation hydration shells are examined. Emphasis is placed on the extent of the effect of the hydrated cation on the cluster properties. Our results show that hydration of Na(+) takes place in the interior of the cluster leading to significant changes in the hydrogen-bond (H-bond) network beyond the first hydration shell. In particular, we find that single acceptor-only H-bond arrangements increase significantly at the surface of the cluster relative to a neat water cluster. The vibrational spectrum of the first hydration shell of the cation, comprised mostly of H-bond double donor-single acceptor water molecules, is similar to that found for water molecules in the interior of a neat water cluster, although a small blue shift of the OH stretching band is observed. Further, a small reduction of the dipole moment of water molecules in the first hydration shell of the cation relative to a neat water cluster is also observed, and this persists to a minor extent when we move from the interior to the surface of the cluster. The present results indicate that the effect of the Na(+) on the cluster properties, although not pronounced, is not constrained to the first hydration shell. The reason appears to lie mostly in the specific orientation of the water molecules in the first coordination sphere, inducing modifications on the H-bond network topology of the cluster.