Kinetics of hydrogen-bond rearrangements in bulk water

Abstract

Molecular dynamics simulations are used to investigate the kinetics of hydrogen-bond rearrangements in bulk water at ambient temperatures. Configurational analyses reveal three distinct bond-breaking processes, two of which constitute rearrangements in the hydrogen-bond network. The kinetic analyses demonstrate the applicability of simple first-order kinetics and reveal a large breadth of time-scales. In agreement with experiments we find that transitions between stable hydrogen-bonded configurations are characterised by an unstable, transient, non-bonded configuration. The overall rate of hydrogen-bond rearrangements is determined as 0.89 ps⁻¹ (1.12 ps), in very good agreement with experimental estimates.