Water in an electric field does not dance alone: The relation between equilibrium structure, time dependent viscosity and molecular motions

• Published in: Journal of molecular liquids Vol. 282; pp. 303 - 315
• Main Authors: Baer, Andreas, Miličević, Zoran, Smith, David M., Smith, Ana-Sunčana
• Format: Journal Article
• Language: English
• Published: Elsevier B.V 15-05-2019
• ISSN: 0167-7322; 1873-3166
• DOI: 10.1016/j.molliq.2019.02.055

Dynamic structuring of water is a key player in a large class of processes underlying biochemical and technological developments today, the latter often involving electric fields. However, the anisotropic coupling between the water structure and the field has not been understood on a molecular level so far. Here we perform extensive molecular dynamics simulations to explore the influence of an externally imposed electric field on liquid water under ambient conditions. Using self-developed analysis tools and rigorous statistical analysis, we unambiguously show that water hydration shells break into subcompartments, which were hitherto not observed due to radial averaging. The shape of subcompartments is sensitive to the field magnitude and affects excitations of the hydrogen bond network including the femtosecond stretching and the sub-picosecond restructuring of hydrogen bonds. Furthermore, by analysing the reorientational dynamics of water molecules, we ascertain the existence of cooperative excitations of small water clusters. Enabled by the interplay between hydrogen bonding, and the coupling of water dipoles to the field, these coordinated motions, occurring on the picosecond time scale, are associated with fluctuations between torque-free states of water dipoles. We show that unlike the coupling between translation and reorientation of water molecules, which takes place on even longer time scales, these coordinated motions are the key for understanding the emergent anisotropy of diffusion and viscosity of water. Particular effort is invested to provide an analysis that allows for future experimental validation.
•Characterized the compartmentalisation of hydration shells of water in E-fields.•Categorized the relaxation of the H-bond network over 4 orders of magnitude in time.•Identified a cooperative relaxation involving small clusters of water molecules.•Associated novel relaxations with the anisotropic transport coefficients of water.•Determined parameters for experimental validation of simulations.