Molecular and collective reorientations in interfacial water are by-and-large decelerated near surfaces subjected to outgoing electric fields (pointing from surface to liquid, i.e., when the surface carries positive charge). In incoming fields at negatively charged surfaces, these rates show a nonmonotonic dependence on field strength where fastest reorientations are observed when the field alignment barely offsets the polarizing effects due to interfacial hydrogen bonding. This extremum coincides with a peak of local static permittivity. We use molecular dynamics simulations to explore the impact of background static field on high frequency AC permittivity in hydration water under an electric field mimicking the conditions inside a capacitor where one of the confinement walls is subject to an outgoing field and the other one to an incoming field. At strong static fields, the absorption peak undergoes a monotonic blue shift upon increasing field strength in both hydration layers. At intermediate fields, however, the hydration region at the wall under an incoming field (the negative capacitor plate) features a red shift coinciding with maximal static-permittivity and reorientation-rate. The shift is mostly determined by the variation of the inverse static dielectric constant as proposed for mono-exponentially decaying polarization correlations. Conversely, hydration water at the opposite (positively charged) surface features a monotonic blue shift consistent with conventional saturation. The sensitivity of absorption peaks on the field suggests that surface charge densities could be deduced from sub-THz dielectric spectroscopy experiments in porous materials when interfaces accommodate a major fraction of water contained in the system.
Polarity-dependence of the nonlinear dielectric response in interfacial water
Molecular dynamics simulations are used to study nonlinear dielectric responses of a confined aqueous film in a planar nanopore under perpendicular electric fields at varied voltages between confining graphene sheets. Dielectric saturation reminiscent of the bulk phase behavior is prevalent at very strong fields, whereas we observe a nonmonotonic permittivity dependence on electric field at intermediate strengths where field-alignment and spontaneous polarization of interfacial water are of comparable magnitudes. The coupling between the two effects results in distinct dielectric responses at opposite confinement walls. The normal component of both the differential dielectric constant and dielectric difference constant tensors averaged over the region closer to the wall under incoming electric field (field pointing from the liquid to the solid phase) initially increases with the strength of the imposed field. The differential permittivity peaks at a field strength previously shown to offset the surface-induced orientation bias of hydration molecules at this wall. Further strengthening of the field results in conventional saturation behavior. At the opposite wall (subject to outgoing field) and in the central region of water slab, the nonlinear dielectric response resembles bulklike saturation. The conditions at the permittivity extremum coincide with the window of accelerated reorientation rates of interfacial water molecules under incoming field uncovered in earlier molecular dynamics analyses.
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- Award ID(s):
- 1800120
- PAR ID:
- 10401635
- Date Published:
- Journal Name:
- The Journal of Chemical Physics
- ISSN:
- 0021-9606
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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