Classification of hydrogen bond flips in small water polyhedra applied to concerted proton tunneling

Abstract

Recently a new mechanism of proton tunneling in a prism-like water hexamer was revealed [Richardson et al., Science, 2016, 351, 1310]. The tunneling motion involves the concerted breaking of two hydrogen bonds and rotations of two nearest water molecules. Eventually, this structural transformation means flipping one of the hydrogen bonds without the creation of defects in the hydrogen bond network. On the surface of polyhedral water clusters, there are five essentially different types of hydrogen bonds, and only two of them can be changed in this manner. In this article, the topological classification of such transformations for five small water polyhedra: triangular, pentagonal, and hexagonal prisms as well as cube and polyhedron 4454, consisting of four square and four pentagonal faces, is presented. Our classification includes the enumeration of all possible one-bond-flips with consideration of the types of hydrogen bonds on the polyhedral surface. Attention is paid to the most stable proton configurations which can be studied in experiments. It was established that a number of one-bond-flip transitions between the low energy configurations are possible in clusters in the shape of triangular and pentagonal prisms.