We present the results of molecular dynamics simulations of a nanoscale electrochemical cell. The simulations include an aqueous electrolyte solution with varying ionic strength (i.e., concentrations ranging from 0-4M) between a pair of metallic electrodes held at constant potential difference. We analyze these simulations by computing the electrostatic potential profile of the electric double-layer region and find it to be nearly independent of ionic concentration, in stark contrast to the predictions of standard continuum-based theories. We attribute this lack of concentration dependence to the molecular influences of water molecules at the electrode-solution interface. These influences include the molecular manifestation of water's dielectric response, which tends to drown out the comparatively weak screening requirement of the ions. To support our analysis, we decompose water's interfacial response into three primary contributions: molecular layering, intrinsic (zero-field) orientational polarization, and the dipolar dielectric response.
more »
« less
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.
more »
« less
- Award ID(s):
- 1800120
- NSF-PAR ID:
- 10401635
- Date Published:
- Journal Name:
- The Journal of Chemical Physics
- ISSN:
- 0021-9606
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
An electric field applied across the interface has been shown to enable transitions from the Cassie to the Wenzel state on superhydrophobic surfaces with miniature corrugations. Molecular dynamics (MD) simulations manifest the possibility of reversible cycling between the two states when narrow surface wells support spontaneous expulsion of water in the absence of the field. With approximately 1 nm sized wells between the surface asperities, the response times to changes in the electric field are of O(0.1) ns, allowing up to GHz frequency of the cycle. Because of the orientation preferences of interfacial water in contact with the solid, the phenomenon depends on the polarity of the field normal to the interface. The threshold field strength for the Cassie-to-Wenzel transition is significantly lower for the field pointing from the aqueous phase to the surface; however, once in the Wenzel state, the opposite field direction secures tighter filling of the wells. Considerable hysteresis revealed by the delayed water retraction at decreasing field strength indicates the presence of moderate kinetic barriers to expulsion. Known to scale approximately with the square of the length scale of the corrugations, these barriers preclude the use of increased corrugation sizes while the reduction of the well diameter necessitates stronger electric fields. Field-controlled Cassie-to-Wenzel transitions are therefore optimized by using superhydrophobic surfaces with nanosized corrugations. Abrupt changes indicate a high degree of cooperativity reflecting the correlations between the wetting states of interconnected wells on the textured surface.more » « less
-
High energy density, high temperature, and low loss polymer dielectrics are highly desirable for electric energy storage, e.g., film capacitors in the power electronics of electric vehicles and high-speed trains. Fundamentally, high polarization and low dielectric loss are two conflicting physical properties, because more polarization processes will involve more loss mechanisms. As such, we can only achieve a delicate balance between high dielectric constant and reasonably low loss. This review focuses on achieving low dielectric loss while trying to enhance dielectric constants for dielectric polymers, which can be divided into two categories: extrinsic and intrinsic. For extrinsic dielectric systems, the working mechanisms include dipolar (e.g., nanodielectrics) and space charge (e.g., ion gels) interfacial polarizations. These polarizations do not increase the intrinsic dielectric constants, but cause decreased breakdown strength and increased dielectric loss for polymers. For intrinsic dielectric polymers, the dielectric constant originates from electronic, atomic (or vibrational), and orientational polarizations, which are intrinsic to the polymers themselves. Because of the nature of molecular bonding for organic polymers, the dielectric constant from electronic and atomic polarizations is limited to 2-5 for hydrocarbon-based insulators (i.e., band gap > 4 eV). It is possible to use orientational polarization to enhance intrinsic dielectric constant while keeping reasonably low loss. However, nonlinear ferroelectric switching in ferroelectric polymers must be avoided. Meanwhile, paraelectric polymers often exhibit high electronic conduction due to large chain motion in the paraelectric phase. In this sense, dipolar glass polymers are more attractive for low loss dielectrics, because frozen chain dynamics enables deep traps to prevent electronic conduction. Both side-chain and main-chain dipolar glass polymers are promising candidates. Furthermore, it is possible to combine intrinsic and extrinsic dielectric properties synergistically in multilayer films to enhance breakdown strength and further reduce dielectric loss for high dielectric constant polar polymers. At last, future research directions are briefly discussed for the ultimate realization of next generation polymer film capacitors.more » « less
-
Electrohydrodynamics of drops is a classic fluid mechanical problem where deformations and microscale flows are generated by application of an external electric field. In weak fields, electric stresses acting on the drop surface drive quadrupolar flows inside and outside and cause the drop to adopt a steady axisymmetric shape. This phenomenon is best explained by the leaky-dielectric model under the premise that a net surface charge is present at the interface while the bulk fluids are electroneutral. In the case of dielectric drops, increasing the electric field beyond a critical value can cause the drop to start rotating spontaneously and assume a steady tilted shape. This symmetry-breaking phenomenon, called Quincke rotation, arises due to the action of the interfacial electric torque countering the viscous torque on the drop, giving rise to steady rotation in sufficiently strong fields. Here, we present a small-deformation theory for the electrohydrodynamics of dielectric drops for the complete Melcher–Taylor leaky-dielectric model in three dimensions. Our theory is valid in the limits of strong capillary forces and highly viscous drops and is able to capture the transition to Quincke rotation. A coupled set of nonlinear ordinary differential equations for the induced dipole moments and shape functions are derived whose solution matches well with experimental results in the appropriate small-deformation regime. Retention of both the straining and rotational components of the flow in the governing equation for charge transport enables us to perform a linear stability analysis and derive a criterion for the applied electric field strength that must be overcome for the onset of Quincke rotation of a viscous drop.more » « less
-
Resonantly enhanced second harmonic generation (SHG) spectra of Coumarin 152 (C152) adsorbed at the water-silica interface show that C152 experiences a local dielectric environment slightly more polar than that of bulk water. This result stands in contrast to recently reported time-resolved fluorescence experiments and simulations that suggest a alkane-like permittivity for interfacial water at strongly associating, hydrophilic solid surfaces. Taken together, these results imply that while the static electric field across the aqueous-silica interface may be large, restricted water dynamics lead to apparent nonpolar solvation behavior similar to that experienced by solutes in confinement. Resonance-enhanced SHG spectra and time-resolved fluorescence of C152 adsorbed to aqueous-hydrophobic silica surfaces show that when water’s ability to hydrogen bond with the silica surface is eliminated, a solute’s interfacial solvation and corresponding ability to photoisomerize converge to an intermediate limit similar to that experienced in bulk acetone or methanol. While water structure and dynamics at solid-liquid interfaces have received considerable attention, results presented below show how strong solvent-substrate interactions can create conflicting pictures of solute reactivity across buried interfaces.more » « less
- Free Publicly Accessible Full Text
-
Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1063/5.0142483
