Hydrogen-Bond Dynamics in the Air−Water Interface

Hydrogen-bond (H-bond) dynamics in the air−water interface is studied by molecular dynamics simulations. The analysis reveals that the dynamics of breaking and forming hydrogen bonds in the air−water interface is faster than that in bulk water for the polarizable water models. This is in contrast to the results found on a protein surface. We show that the difference stems from more rapid translational diffusion in the interface. When the effect of pair diffusion is eliminated, the hydrogen-bond dynamics in the interface is observed to be slower than that in the bulk. This occurs because the number of water molecules adjacent to a hydrogen-bonded pair and available to accept or donate a hydrogen bond is smaller in the interface than in the bulk. The comparison between polarizable water models and fixed-charge models highlights the potential importance of the polarization effect in the water−vapor interface.