Concerted Hydrogen-Bond Breaking by Quantum Tunneling in the Water Hexamer Prism

Authors

Jeremy O. Richardson, University of Cambridge
Cristobal Perez, University of VirginiaFollow
Simon Lobsiger, University of Virginia
Adam A. Reid, University of Cambridge
Berhane Temelso, Bucknell UniversityFollow
George C. Shields, Bucknell UniversityFollow
Zbigniew Kisiel, Polish Academy of Sciences
David J. Wales, University of Cambridge
Brooks H. Pate, University of Virginia
Stuart C. Althorpe, University of Cambridge

Publication Date

2016

Description

The nature of the intermolecular forces between water molecules is the same in small hydrogen-bonded clusters as in the bulk. The rotational spectra of the clusters therefore give insight into the intermolecular forces present in liquid water and ice. The water hexamer is the smallest water cluster to support low-energy structures with branched three-dimensional

hydrogen-bond networks, rather than cyclic two-dimensional topologies. Here we report measurements of splitting patterns in rotational transitions of the water hexamer prism, and we used quantum simulations to show that they result from geared and antigeared rotations of a pair of water molecules. Unlike previously reported tunneling motions in water clusters, the geared motion involves the concerted breaking of two hydrogen bonds. Similar types of motion may be feasible in interfacial and confined water.

Journal

Science

Volume

351

Issue

6279

First Page

1310

Last Page

1313

Department

Chemistry

Link to Published Version

http://science.sciencemag.org/content/351/6279/1310

DOI

10.1126/science.aae0012

Recommended Citation

Richardson, Jeremy O.; Perez, Cristobal; Lobsiger, Simon; Reid, Adam A.; Temelso, Berhane; Shields, George C.; Kisiel, Zbigniew; Wales, David J.; Pate, Brooks H.; and Althorpe, Stuart C.. "Concerted Hydrogen-Bond Breaking by Quantum Tunneling in the Water Hexamer Prism." Science (2016) : 1310-1313.