Towards a unified description of the hydrogen bond network of liquid water: A dynamics based approach

Journal Article · Wed Dec 03 00:00:00 EST 2014 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.4902538· OSTI ID:1420501

Ozkanlar, Abdullah; Zhou, Tiecheng; Clark, Aurora E.

The definition of a hydrogen bond (H-bond) is intimately related to the topological and dynamic properties of the hydrogen bond network within liquid water. The development of a universal H-bond definition for water is an active area of research as it would remove many ambiguities in the network properties that derive from the fixed definition employed to assign whether a water dimer is hydrogen bonded. This work investigates the impact that an electronic-structure based definition, an energetic, and a geometric definition of the H-bond has upon both topological and dynamic network behavior of simulated water. In each definition, the use of a cutoff (either geometric or energetic) to assign the presence of a H-bond leads to the formation of transiently bonded or broken dimers, which have been quantified within the simulation data. The relative concentration of transient species, and their duration, results in two of the three definitions sharing similarities in either topological or dynamic features (H-bond distribution, H-bond lifetime, etc.), however no two definitions exhibit similar behavior for both classes of network properties. In fact, two networks with similar local network topology (as indicated by similar average H-bonds) can have dramatically different global network topology (as indicated by the defect state distributions) and altered H-bond lifetimes. A dynamics based correction scheme is then used to remove artificially transient H-bonds and to repair artificially broken bonds within the network such that the corrected network exhibits the same structural and dynamic properties for two H-bond definitions (the properties of the third definition being significantly improved). The algorithm described represents a significant step forward in the development of a unified hydrogen bond network whose properties are independent of the original hydrogen bond definition that is employed.

• Sponsoring Organization: USDOE Office of Science (SC), Basic Energy Sciences (BES)
• Grant/Contract Number: DESC0001815
• OSTI ID: 1420501
• Journal Information: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Vol. 141 Journal Issue: 21; ISSN 0021-9606
• Publisher: American Institute of Physics
• Country of Publication: United States
• Language: English