The statistics of electric field fluctuations in liquid water

Abstract

Electric field fluctuations play a major role in dissociation reactions in liquid water and determine its vibrational spectroscopic response. Here, we study the statistics of electric fields in liquid water using molecular dynamics computer simulations with particular focus on the strong but rare fields that drive dissociation. Our simulations indicate that the important contributions to the electric field acting on OH bonds stem from water molecules less than 7 Å away. Long-ranged contributions play a minor role.

Keywords:

• water
• molecular dynamics simulation
• autoionisation
• electric field fluctuations

Acknowledgements

This work was supported by the Austrian Science Fund (FWF) under grant P20942-N16 and the Science College Computational Materials Science under grant W004, and by the University of Vienna through the University Focus Research Area Materials Science (project ‘Multi-scale Simulations of Materials Properties and Processes in Materials’).