Structural Parameters and Thermodynamics of the Formation of Molecular Water Clusters

Abstract

The formation of molecular water clusters is simulated using the theoretical density functional theory/ B3LYP/6-311+G(d,p) method. The spatial configurations of 29 clusters with 2 to 28 water molecules are calculated. The dipole moments, the complete complex-formation enthalpy, and the enthalpy of the successive joining of water molecules are determined with the basis-set superposition error taken into account. The features of the geometric structure and the hydrogen-bond strength of water clusters are analyzed on the basis of the obtained theoretical data. The complex-formation enthalpy is revealed to depend periodically on the number of water molecules in a cluster. It is found that clusters with molecules whose number is a multiple of four are energetically most advantageous. When a molecular cluster is built starting with 17 molecules, the cluster structure is changed, resulting in that one end of the complex rolls up into a prismatic configuration.