Impedance of nanocapacitors from molecular simulations to understand the dynamics of confined electrolytes.

Nanoelectrochemical devices have become a promising candidate technology across various applications, including sensing and energy storage, and provide new platforms for studying fundamental properties of electrode/electrolyte interfaces. In this work, we employ constant-potential molecular dynamics simulations to investigate the impedance of gold-aqueous electrolyte nanocapacitors, exploiting a recently introduced fluctuation-dissipation relation. In particular, we relate the frequency-dependent impedance of these nanocapacitors to the complex conductivity of the bulk electrolyte in different regimes, and use this connection to design simple but accurate equivalent circuit models. We show that the electrode/electrolyte interfacial contribution is essentially capacitive and that the electrolyte response is bulk-like even when the interelectrode distance is only a few nanometers, provided that the latter is sufficiently large compared to the Debye screening length. We extensively compare our simulation results with spectroscopy experiments and predictions from analytical theories. In contrast to experiments, direct access in simulations to the ionic and solvent contributions to the polarization allows us to highlight their significant and persistent anticorrelation and to investigate the microscopic origin of the timescales observed in the impedance spectrum. This work opens avenues for the molecular interpretation of impedance measurements, and offers valuable contributions for future developments of accurate coarse-grained representations of confined electrolytes.

The limit of macroscopic homogeneous ice nucleation at the nanoscale.

Nucleation in small volumes of water has garnered renewed interest due to the relevance of pore condensation and freezing under conditions of low partial pressures of water, such as in the upper troposphere. Molecular simulations can in principle provide insight on this process at the molecular scale that is challenging to achieve experimentally. However, there are discrepancies in the literature as to whether the rate in confined systems is enhanced or suppressed relative to bulk water at the same temperature and pressure. In this study, we investigate the extent to which the size of the critical nucleus and the rate at which it grows in thin films of water are affected by the thickness of the film. Our results suggest that nucleation remains bulk-like in films that are barely large enough accommodate a critical nucleus. This conclusion seems robust to the presence of physical confining boundaries. We also discuss the difficulties in unambiguously determining homogeneous nucleation rates in nanoscale systems, owing to the challenges in defining the volume. Our results suggest any impact on a film's thickness on the rate is largely inconsequential for present day experiments.

Classical Quantum Friction at Water-Carbon Interfaces.

Friction at water-carbon interfaces remains a major puzzle with theories and simulations unable to explain experimental trends in nanoscale waterflow. A recent theoretical framework─quantum friction (QF)─proposes to resolve these experimental observations by considering nonadiabatic coupling between dielectric fluctuations in water and graphitic surfaces. Here, using a classical model that enables fine-tuning of the solid's dielectric spectrum, we provide evidence from simulations in general support of QF. In particular, as features in the solid's dielectric spectrum begin to overlap with water's librational and Debye modes, we find an increase in friction in line with that proposed by QF. At the microscopic level, we find that this contribution to friction manifests more distinctly in the dynamics of the solid's charge density than that of water. Our findings suggest that experimental signatures of QF may be more pronounced in the solid's response rather than liquid water's.

Remembering the Work of Phillip L. Geissler: A Coda to His Scientific Trajectory.

Phillip L. Geissler made important contributions to the statistical mechanics of biological polymers, heterogeneous materials, and chemical dynamics in aqueous environments. He devised analytical and computational methods that revealed the underlying organization of complex systems at the frontiers of biology, chemistry, and materials science. In this retrospective we celebrate his work at these frontiers.

A theory for the stabilization of polar crystal surfaces by a liquid environment.

Polar crystal surfaces play an important role in the functionality of many materials and have been studied extensively over many decades. In this article, a theoretical framework is presented that extends existing theories by placing the surrounding solution environment on an equal footing with the crystal itself; this is advantageous, e.g., when considering processes such as crystal growth from solution. By considering the polar crystal as a stack of parallel plate capacitors immersed in a solution environment, the equilibrium adsorbed surface charge density is derived by minimizing the free energy of the system. In analogy to the well-known diverging surface energy of a polar crystal surface at zero temperature, for a crystal in solution it is shown that the "polar catastrophe" manifests as a diverging free energy cost to perturb the system from equilibrium. Going further than existing theories, the present formulation predicts that fluctuations in the adsorbed surface charge density become increasingly suppressed with increasing crystal thickness. We also show how, in the slab geometry often employed in both theoretical and computational studies of interfaces, an electric displacement field emerges as an electrostatic boundary condition, the origins of which are rooted in the slab geometry itself, rather than the use of periodic boundary conditions. This aspect of the work provides a firmer theoretical basis for the recent observation that standard "slab corrections" fail to correctly describe, even qualitatively, polar crystal surfaces in solution.

Dielectric response of thin water films: a thermodynamic perspective.

The surface of a polar liquid presents a special environment for the solvation and organization of charged solutes, which differ from bulk behaviors in important ways. These differences have motivated many attempts to understand electrostatic response at aqueous interfaces in terms of a spatially varying dielectric permittivity, typically concluding that the dielectric constant of interfacial water is significantly lower than in the bulk liquid. Such analyses, however, are complicated by the potentially nonlocal nature of dielectric response over the short length scales of interfacial heterogeneity. Here we circumvent this problem for thin water films by adopting a thermodynamic approach. Using molecular simulations, we calculate the solvent's contribution to the reversible work of charging a parallel plate capacitor. We find good agreement with a simple dielectric continuum model that assumes bulk dielectric permittivity all the way up to the liquid's boundary, even for very thin (∼1 nm) films. This comparison requires careful attention to the placement of dielectric boundaries between liquid and vapor, which also resolves apparent discrepancies with dielectric imaging experiments.

Can molecular simulations reliably compare homogeneous and heterogeneous ice nucleation?

In principle, the answer to the posed titular question is undoubtedly "yes." But in practice, requisite reference data for homogeneous systems have been obtained with a treatment of intermolecular interactions that is different from that typically employed for heterogeneous systems. In this article, we assess the impact of the choice of truncation scheme when comparing water in homogeneous and inhomogeneous environments. Specifically, we use explicit free energy calculations and a simple mean field analysis to demonstrate that using the "cut-and-shift" version of the Lennard-Jones potential (common to most simple point charge models of water) results in a systematic increase in the melting temperature of ice Ih. In addition, by drawing an analogy between a change in cutoff and a change in pressure, we use existing literature data for homogeneous ice nucleation at negative pressures to suggest that enhancements due to heterogeneous nucleation may have been overestimated by several orders of magnitude.

Reconstructing animated eye movements from electrooculography data to aid the diagnosis of vestibular disorders.

OBJECTIVE: To develop a method of visualising electrooculography data to improve the interpretability of nystagmus eye-movements captured using the Continuous Ambulatory Vestibular Assessment (CAVA®) device. DESIGN: We are currently undertaking a clinical investigation to evaluate the capabilities of the CAVA® device to detect periods of pathological nystagmus. The work presented here was undertaken using unblinded data obtained from the preliminary phase of this investigation. STUDY SAMPLE: One patient with Ménière's disease and one with Benign Paroxysmal Positional Vertigo. RESULTS: Using the electrooculography data captured by the CAVA® device, we reconstructed 2D animations of patients' eye movements during attacks of vertigo. We were able to reanimate nystagmus produced as a consequence of two conditions. Concurrent video footage showed that the animations were visually very similar to the patient's actual eye-movements, excepting torsional eye-movements. CONCLUSIONS: The reconstructed animations provide an alternative presentation modality, enabling clinicians to largely interpret electrooculography data as if they were present during a vertigo attack. We were able to recreate nystagmus from attacks experienced in the community rather than a clinical setting. This information provides an objective record of a patient's nystagmus and could be used to complement a full neurotologic history when considering diagnosis and treatment options.

Quadrupole-mediated dielectric response and the charge-asymmetric solvation of ions in water.

Treating water as a linearly responding dielectric continuum on molecular length scales allows very simple estimates of the solvation structure and thermodynamics for charged and polar solutes. While this approach can successfully account for basic length and energy scales of ion solvation, computer simulations indicate not only its quantitative inaccuracies but also its inability to capture some basic and important aspects of microscopic polarization response. Here, we consider one such shortcoming, a failure to distinguish the solvation thermodynamics of cations from that of otherwise-identical anions, and we pursue a simple, physically inspired modification of the dielectric continuum model to address it. The adaptation is motivated by analyzing the orientational response of an isolated water molecule whose dipole is rigidly constrained. Its free energy suggests a Hamiltonian for dipole fluctuations that accounts implicitly for the influence of higher-order multipole moments while respecting constraints of molecular geometry. We propose a field theory with the suggested form, whose nonlinear response breaks the charge symmetry of ion solvation. An approximate variational solution of this theory, with a single adjustable parameter, yields solvation free energies that agree closely with simulation results over a considerable range of solute size and charge.

Detecting positional vertigo using an ensemble of 2D convolutional neural networks.

The aim of the work presented here was to develop a system that can automatically identify attacks of dizziness occurring in patients suffering from positional vertigo, which occurs when sufferers move their head into certain positions. We used our novel medical device, CAVA, to record eye- and head-movement data continually for up to 30 days in patients diagnosed with a disorder called Benign Paroxysmal Positional Vertigo. Building upon our previous work, we describe a novel ensemble of five 2D Convolutional Neural Networks, using composite recognition features, including eye-movement data and three-channel accelerometer data. We achieve an F 1 score of 0.63 across an 11-fold cross-fold validation experiment, demonstrating that the system can detect a few seconds of motion provoked dizziness from within over a 100 h of normal eye-movement data. We show that the system outperforms our previous 1D Neural Network approach, and that our ensemble classifier is superior to each of the individual networks it contains. We also demonstrate that our composite recognition features provide improved performance over results obtained using the individual data sources independently.

Microscopic Kinetics Pathway of Salt Crystallization in Graphene Nanocapillaries.

The fundamental understanding of crystallization, in terms of microscopic kinetic and thermodynamic details, remains a key challenge in the physical sciences. Here, by using in situ graphene liquid cell transmission electron microscopy, we reveal the atomistic mechanism of NaCl crystallization from solutions confined within graphene cells. We find that rock salt NaCl forms with a peculiar hexagonal morphology. We also see the emergence of a transitory graphitelike phase, which may act as an intermediate in a two-step pathway. With the aid of density functional theory calculations, we propose that these observations result from a delicate balance between the substrate-solute interaction and thermodynamics under confinement. Our results highlight the impact of confinement on both the kinetics and thermodynamics of crystallization, offering new insights into heterogeneous crystallization theory and a potential avenue for materials design.

Clinical Techniques and Technology: Vestibular Telemetry.

When a patient presents to a clinician with dizziness, it can be difficult for the patient to describe their symptoms in a clear manner, and clinical examination often yields entirely normal results. Ideally, it would be favorable to measure key physiological parameters during their episodes of dizziness. From a clinical perspective, this would allow a more timely and more accurate diagnosis. From a research perspective, it would allow a greater understanding of how the vestibular system malfunctions as a consequence of vestibular disease. The authors of this report have been funded by the UK Medical Research Council to develop and test a novel technology to measure, record, and analyze key physiological parameters provided by the dizzy individual during an episode of dizziness while active in the community. We provide the context to evolving work in this field, the outcome of preliminary studies, and a consideration of future opportunities.

1D Convolutional Neural Networks for Detecting Nystagmus.

Vertigo is a type of dizziness characterised by the subjective feeling of movement despite being stationary. One in four individuals in the community experience symptoms of dizziness at any given time, and it can be challenging for clinicians to diagnose the underlying cause. When dizziness is the result of a malfunction in the inner-ear, the eyes flicker and this is called nystagmus. In this article we describe the first use of Deep Neural Network architectures applied to detecting nystagmus. The data used in these experiments was gathered during a clinical investigation of a novel medical device for recording head and eye movements. We describe methods for training networks using very limited amounts of training data, with an average of 11 mins of nystagmus across four subjects, and less than 24 hours of data in total, per subject. Our methods work by replicating and modifying existing samples to generate new data. In a cross-fold validation experiment, we achieve an average F1 score of 0.59 (SD = 0.24) across all four folds, showing that the methods employed are capable of identifying periods of nystagmus with a modest degree of accuracy. Notably, we were also able to identify periods of pathological nystagmus produced by a patient during an acute attack of Ménière's Disease, despite training the network on nystagmus that was induced by different means.

Nystagmus during an acute Ménière's attack: from prodrome to recovery.

OBJECTIVE: We are currently undertaking a clinical investigation to evaluate the diagnostic capability of a system for detecting periods of pathological dizziness. This article presents an analysis of the data captured during an acute attack of Ménière's disease. DESIGN: The Continuous Ambulatory Vestibular Assessment (CAVA) device is worn by patients in the community, and continuously records eye and head movement data (vestibular telemetry). STUDY SAMPLE: A 53-year-old lady with a fifteen-year history of left-sided unilateral Ménière's disease. RESULTS: The patient wore the device nearly continuously for thirty days. The data revealed a three-hour long attack of vertigo consisting of four separate phases of nystagmus. The duration, beat-direction and slow phase velocity of the nystagmus evolved through time. The first phase contained isolated nystagmus beats which preceded the patient's record of the vertigo attack onset but coincided with anticipation of an impending vertigo attack. CONCLUSIONS: CAVA provides a unique insight into the physiological parameters present during episodes of dizziness. Here, it has provided the first full example of an acute Ménière's attack, including a period of prodrome. These findings have implications for the prediction of vertigo attack onset, for the diagnosis of Ménière's disease and other diseases resulting in dizziness.

Macroscopic surface charges from microscopic simulations.

Attaining accurate average structural properties in a molecular simulation should be considered a prerequisite if one aims to elicit meaningful insights into a system's behavior. For charged surfaces in contact with an electrolyte solution, an obvious example is the density profile of ions along the direction normal to the surface. Here, we demonstrate that, in the slab geometry typically used in simulations, imposing an electric displacement field D determines the integrated surface charge density of adsorbed ions at charged interfaces. This allows us to obtain macroscopic surface charge densities irrespective of the slab thickness used in our simulations. We also show that the commonly used Yeh-Berkowitz method and the "mirrored slab" geometry both impose vanishing integrated surface charge densities. We present results both for relatively simple rocksalt (1 1 1) interfaces and the more complex case of kaolinite's basal faces in contact with an aqueous electrolyte solution.