Quadrupolar 23^{23}Na+^{+} NMR Relaxation as a Probe of Subpicosecond Collective Dynamics in Aqueous Electrolyte Solutions

Nuclear magnetic resonance relaxometry represents a powerful tool for extracting dynamic information. Yet, obtaining links to molecular motion is challenging for many ions that relax through the quadrupolar mechanism, which is mediated by electric field gradient fluctuations and lacks a detailed microscopic description. For sodium ions in aqueous electrolytes, we combine ab initio calculations to account for electron cloud effects with classical molecular dynamics to sample long-time fluctuations, and obtain relaxation rates in good agreement with experiments over broad concentration and temperature ranges. We demonstrate that quadrupolar nuclear relaxation is sensitive to subpicosecond dynamics not captured by previous models based on water reorientation or cluster rotation. While ions affect the overall water retardation, experimental trends are mainly explained by dynamics in the first two solvation shells of sodium, which contain mostly water. This work thus paves the way to the quantitative understanding of quadrupolar relaxation in electrolyte and bioelectrolyte systems.Comment: 36 pages, 25 figures, supplementary information include

Topology-Based Detection and Tracking of Deadlocks Reveal Aging of Active Ring Melts

Connecting the viscoelastic behavior of stressed ring melts to the various forms of entanglement that can emerge in such systems is still an open challenge. Here, we consider active ring melts, where stress is generated internally, and introduce a topology-based method to detect and track consequential forms of ring entanglements, namely, deadlocks. We demonstrate that, as stress accumulates, more and more rings are co-opted in a growing web of deadlocks that entrap many other rings by threading, bringing the system to a standstill. The method ought to help the study of topological aging in more general polymer contexts

Electrical noise in electrolytes: a theoretical perspective

Seemingly unrelated experiments such as electrolyte transport through nanotubes, nano-scale electrochemistry, NMR relaxometry and surface force balance measurements, all probe electrical fluctuations: of the electric current, the charge and polarization, the field gradient (for quadrupolar nuclei) and the coupled mass/charge densities. The fluctuations of such various observables arise from the same underlying microscopic dynamics of the ions and solvent molecules. In principle, the relevant length and time scales of these dynamics are encoded in the dynamic structure factors. However, modelling the latter for frequencies and wavevectors spanning many orders of magnitude remains a great challenge to interpret the experiments in terms of physical processes such as solvation dynamics, diffusion, electrostatic and hydrodynamic interactions between ions, interactions with solid surfaces, etc. Here, we highlight the central role of the charge–charge dynamic structure factor in the fluctuations of electrical observables in electrolytes and offer a unifying perspective over a variety of complementary experiments. We further analyze this quantity in the special case of an aqueous NaCl electrolyte, using simulations with explicit ions and an explicit or implicit solvent. We discuss the ability of the standard Poisson–Nernst–Planck theory to capture the simulation results, and how the predictions can be improved. We finally discuss the contributions of ions and water to the total charge fluctuations. This work illustrates an ongoing effort towards a comprehensive understanding of electrical fluctuations in bulk and confined electrolytes, in order to enable experimentalists to decipher the microscopic properties encoded in the measured electrical noise

MetalWalls: Simulating electrochemical interfaces between polarizable electrolytes and metallic electrodes

Electrochemistry is central to many applications, ranging from biology to energy science. Studies now involve a wide range of techniques, both experimental and theoretical. Modelling and simulations methods, such as density functional theory or molecular dynamics, provide key information on the structural and dynamic properties of the systems. Of particular importance are polarization effects the electrode/electrolyte interface, which are difficult to simulate accurately. Here we show how these electrostatic interactions are taken into account in the framework of the Ewald summation method. We discuss, in particular, the formal set up for calculations that enforce periodic boundary conditions in two directions, a geometry that more closely reflects the characteristics of typical electrolyte/electrode systems and presents some differences with respect to the more common case of periodic boundary conditions in three dimensions. These formal developments are implemented and tested in MetalWalls, a molecular dynamics software which captures the polarization of the electrolyte and allows the simulation of electrodes maintained at a constant potential. We also discuss the technical aspects involved in the calculation of two sets of coupled degrees of freedom, namely the induced dipoles and the electrode charges. We validate the implementation, first on simple systems, then on the well-known interface between graphite electrodes and a room-temperature ionic liquid. We finally illustrate the capabilities of MetalWalls by studying the adsorption of a complex functionalized electrolyte on a graphite electrode

MetalWalls: Simulating electrochemical interfaces between polarizable electrolytes and metallic electrodes

International audienceElectrochemistry is central to many applications, ranging from biology to energy science. Studies now involve a wide range of techniques, both experimental and theoretical. Modeling and simulations methods, such as density functional theory or molecular dynamics, provide key information on the structural and dynamic properties of the systems. Of particular importance are polarization effects of the electrode/electrolyte interface, which are difficult to simulate accurately. Here, we show how these electrostatic interactions are taken into account in the framework of the Ewald summation method. We discuss, in particular, the formal setup for calculations that enforce periodic boundary conditions in two directions, a geometry that more closely reflects the characteristics of typical electrolyte/electrode systems and presents some differences with respect to the more common case of periodic boundary conditions in three dimensions. These formal developments are implemented and tested in MetalWalls, a molecular dynamics software that captures the polarization of the electrolyte and allows the simulation of electrodes maintained at a constant potential. We also discuss the technical aspects involved in the calculation of two sets of coupled degrees of freedom, namely the induced dipoles and the electrode charges. We validate the implementation, first on simple systems, then on the well-known interface between graphite electrodes and a room-temperature ionic liquid. We finally illustrate the capabilities of MetalWalls by studying the adsorption of a complex functionalized electrolyte on a graphite electrode

Ring polymers are much stronger depleting agents than linear ones

We investigate the conformations and shapes of circular polymers close to planar, hard walls as well as the ensuing ring–wall and polymer-induced wall–wall interactions in ring polymer solutions. We derive, by means of Monte Carlo simulations, the effective interaction potential between the centres of mass of flexible, unknotted ring polymers and a hard wall for different polymerisation degrees N. Adopting the coarse-grained description of ring polymers as ultrasoft, penetrable spheres, mean-field density functional theory is then employed in order to examine ring polymer solutions under confinement. We demonstrate that, below the semi-dilute regime, ring polymers structure close to walls much more strongly than their linear counterparts, their density profiles featuring pronounced oscillations. Moreover, the polymer-induced depletion potential between the two walls exhibits an oscillatory profile reminiscent of hard-sphere systems, with oscillations that intensify upon increasing polymer concentration. The obtained form of the depletion interaction is shown to be qualitatively different in comparison to the case of linear polymer solutions at the corresponding densities.© 2018 The Author(s