Electric field of DNA in solution: who is in charge?

In solution, DNA is a highly charged macromolecule which bears a unit of negative charge on each phosphate of its sugar-phosphate backbone. Although partially compensated by counterions adsorbed at or condensed near it, DNA still produces a substantial electric field in its vicinity, which is screened by buffer electrolyte at longer distances from the DNA. Such field has been explored so far predominantly within the scope of a primitive model of the electrolytic solution, not considering more complicated structural effects of the water solvent. In this paper we investigate the distribution of electric field around DNA using linear response nonlocal electrostatic theory, applied here for helix-specific charge distributions, and compare the predictions of such theory with specially performed fully atomistic large scale molecular dynamics simulations. The main finding of this study is that oscillations in the electrostatic potential distribution are present around DNA, caused by the overscreening effect of structured water. Surprisingly, electrolyte ions at physiological concentrations do not strongly disrupt these oscillations, and rather distribute according to these oscillating patterns, indicating that water structural effects dominate the short-range electrostatics. We also show that (i) structured water adsorbed in the grooves of DNA lead to a positive electrostatic potential core, (ii) the Debye length some 10 {\AA} away from the DNA is reduced, effectively renormalised by the helical pitch of the DNA, and (iii) Lorentzian contributions to the nonlocal dielectric function of water, effectively reducing the dielectric constant close to the DNA, enhances the overall electric field. The impressive agreement between the atomistic simulations and the developed theory substantiates the use of nonlocal electrostatics when considering solvent effects in molecular processes in biology.

Ionotronics for reverse actuation.

In the midst of an ongoing energy crisis, the search for new methods of energy harvesting has never been more important. Here we explore, analyse and discuss principles of ionotronic reverse-actuator devices based on the effect of double-layer charging. The designs that we consider in this paper operate based on a common principle - using external mechanical work, which would otherwise be wasted, to produce changes in the contact area of electrode and electrolyte, translated into the time variation of the double-layer capacitance. Periodic variation of capacitance, when connected to a reference voltage source, produces alternating electric current through a load. This concept is not new and in some forms was realised in the early works of Boland, Krupenkin and several papers of our group. The goal of the present paper is to build a comprehensive analytical platform for a description of operation of such devices in terms of materials, generated power as a function of the frequency of variation of applied force, electrical load, and other factors; the understanding of which allows us to optimise these systems and navigate their construction. The first design, discussed in the paper, is based on flat electrodes. It is the simplest one and, as such, helps elucidate some key factors determining power generation. While being easy to realise experimentally, it generates relatively low power, even when optimised. The second design, based on microporous electrodes is more sophisticated and allows a much larger power harvest. The results are also compared to the recently proposed capacitive rotor device. The developed theory is set to capture the key factors that determine the functioning of the considered reverse actuators. The structures under study are matched to fit into the sole of a shoe and produce power from walking and running. However, they can also be scaled-up to larger operating systems and various external loads.

Orientational Ordering in Nano-confined Polar Liquids.

Water and other polar liquids exhibit nanoscale structuring near charged interfaces. When a polar liquid is confined between two charged surfaces, the interfacial solvent layers begin to overlap, resulting in solvation forces. Here, we perform molecular dynamics simulations of polar liquids with different dielectric constants and molecular shapes and sizes confined between charged surfaces, demonstrating strong orientational ordering in the nanoconfined liquids. To rationalize the observed structures, we apply a coarse-grained continuum theory that captures the orientational ordering and solvation forces of those liquids. Our findings reveal the subtle behavior of different nanoconfined polar liquids and establish a simple law for the decay length of the interfacial orientations of the solvents, which depends on their molecular size and polarity. These insights shed light on the nature of solvation forces, which are important in colloid and membrane science, scanning probe microscopy, and nano-electrochemistry.

Theory and Simulations of Ionic Liquids in Nanoconfinement.

Room-temperature ionic liquids (RTILs) have exciting properties such as nonvolatility, large electrochemical windows, and remarkable variety, drawing much interest in energy storage, gating, electrocatalysis, tunable lubrication, and other applications. Confined RTILs appear in various situations, for instance, in pores of nanostructured electrodes of supercapacitors and batteries, as such electrodes increase the contact area with RTILs and enhance the total capacitance and stored energy, between crossed cylinders in surface force balance experiments, between a tip and a sample in atomic force microscopy, and between sliding surfaces in tribology experiments, where RTILs act as lubricants. The properties and functioning of RTILs in confinement, especially nanoconfinement, result in fascinating structural and dynamic phenomena, including layering, overscreening and crowding, nanoscale capillary freezing, quantized and electrotunable friction, and superionic state. This review offers a comprehensive analysis of the fundamental physical phenomena controlling the properties of such systems and the current state-of-the-art theoretical and simulation approaches developed for their description. We discuss these approaches sequentially by increasing atomistic complexity, paying particular attention to new physical phenomena emerging in nanoscale confinement. This review covers theoretical models, most of which are based on mapping the problems on pertinent statistical mechanics models with exact analytical solutions, allowing systematic analysis and new physical insights to develop more easily. We also describe a classical density functional theory, which offers a reliable and computationally inexpensive tool to account for some microscopic details and correlations that simplified models often fail to consider. Molecular simulations play a vital role in studying confined ionic liquids, enabling deep microscopic insights otherwise unavailable to researchers. We describe the basics of various simulation approaches and discuss their challenges and applicability to specific problems, focusing on RTIL structure in cylindrical and slit confinement and how it relates to friction and capacitive and dynamic properties of confined ions.

Energy Storage Mechanism in Supercapacitors with Porous Graphdiynes: Effects of Pore Topology and Electrode Metallicity.

Porous graphdiynes are a new class of porous 2D materials with tunable electronic structures and various pore structures. They have potential applications as well-defined nanostructured electrodes and can provide platforms for understanding energy storage mechanisms underlying supercapacitors. Herein, the effect of stacking structure and metallicity on energy storage with such electrodes is investigated. Simulations reveal that supercapacitors based on porous graphdiynes of AB stacking structure can achieve both higher double-layer capacitance and ionic conductivity than AA stacking. This phenomenon is ascribed to more intense image forces in AB stacking, leading to a breakdown of ionic ordering and the formation of effective "free ions". Macroscale analysis shows that doped porous graphdiynes can deliver outstanding gravimetric and volumetric energy and power densities due to their enhanced quantum capacitance. These findings pave the way for designing high-performance supercapacitors by regulating pore topology and metallicity of electrode materials.

Less Is More: Can Low Quantum Capacitance Boost Capacitive Energy Storage?

We present a theoretical analysis of charge storage in electrochemical capacitors with electrodes based on carbon nanotubes. Using exact analytical solutions supported by Monte Carlo simulations, we show how the limitations of the electron density of states in such low-dimensional electrode materials may help boost the energy stored at increased voltages. While these counterintuitive predictions await experimental verification, they suggest exciting opportunities for enhancing energy storage by rational engineering of the electronic properties of low-dimensional electrodes.

Gelation, clustering, and crowding in the electrical double layer of ionic liquids.

Understanding the bulk and interfacial properties of super-concentrated electrolytes, such as ionic liquids (ILs), has attracted significant attention lately for their promising applications in supercapacitors and batteries. Recently, McEldrew et al. [J. Phys. Chem. B 125, 2677 (2021)] developed a theory for reversible ion associations in bulk ILs, which accounted for the formation of all possible (Cayley tree) clusters and a percolating ionic network (gel). Here, we adopt and develop this approach to understand the associations of ILs in the electrical double layer at electrified interfaces. With increasing charge of the electrode, the theory predicts a transition from a regime dominated by a gelled or clustered state to a crowding regime dominated by free ions. This transition from gelation to crowding is conceptually similar to the overscreening to crowding transition.

Electrochemically controlled rectification in symmetric single-molecule junctions.

Single-molecule electrochemical science has advanced over the past decades and now extends well beyond molecular imaging, to molecular electronics functions such as rectification and amplification. Rectification is conceptually the simplest but has involved mostly challenging chemical synthesis of asymmetric molecular structures or asymmetric materials and geometry of the two enclosing electrodes. Here we propose an experimental and theoretical strategy for building and tuning in situ (in operando) rectification in two symmetric molecular structures in electrochemical environment. The molecules were designed to conduct electronically via either their lowest unoccupied molecular orbital (LUMO; electron transfer) or highest occupied molecular orbital (HOMO; "hole transfer"). We used a bipotentiostat to control separately the electrochemical potential of the tip and substrate electrodes of an electrochemical scanning tunneling microscope (EC-STM), which leads to independent energy alignment of the STM tip, the molecule, and the STM substrate. By creating an asymmetric energy alignment, we observed single-molecule rectification of each molecule within a voltage range of ±0.5 V. By varying both the dominating charge transporting LUMO or HOMO energy and the electrolyte concentration, we achieved tuning of the polarity as well as the amplitude of the rectification. We have extended an earlier proposed theory that predicts electrolyte-controlled rectification to rationalize all the observed in situ rectification features and found excellent agreement between theory and experiments. Our study thus offers a way toward building controllable single-molecule rectifying devices without involving asymmetric molecular structures.

Optical response of hyperbolic metamaterials with adsorbed nanoparticle arrays.

Experimental studies of have been recently performed to determine the optical effect of adsorption of arrays of gold nanoparticles, NPs (16 nm or 40 nm in diameter) on reflective substrates (Ma et al., ACS Photonics, 2018, 5, 4604-4616; Ma et al., ACS Nano, 2020, 14, 328-336) and on transparent interfaces (Montelongo et al., Nat. Mater., 2017, 16, 1127-1135). As predicted by the theory (Sikdar et al., Phys. Chem. Chem. Phys., 2016, 18, 20486-20498), a reflection quenching effect was observed on the reflective substrates, in the frequency domain centred around the nanoparticle localised plasmon resonance. Those results showed a broad dip in reflectivity, which was deepening and red-shifting with increasing array densities. In contrast, the second system has shown, also in accordance with the theory (Sikdar and Kornyshev, Sci. Rep., 2016, 6, 1-16), a broad reflectivity peak in the same frequency domain, increasing in intensity and shifting to the red with densification of the array. In the present paper, we develop a theory of an optical response of NP arrays adsorbed on the surface of stacked nanosheet hyperbolic substrates. The response varies between quenched and enhanced reflectivity, depending on the volume fractions of the metallic and dielectric components in the hyperbolic metamaterial. We reproduce the results of the earlier works in the two opposite limiting cases - of a pure metal and a pure dielectric substrates, while predicting novel resonances for intermediate compositions. Whereas the metal/dielectric ratio in the hyperbolic substrate cannot be changed in time - for each experiment a new substrate should be fabricated - the density of the adsorbed nanoparticle arrays can be controlled in real time in electrochemical photonic cells (Montelongo et al., Nat. Mater., 2017, 16, 1127-1135; Ma et al., ACS Photonics, 2018, 5, 4604-4616; Ma et al., ACS Nano, 2020, 14, 328-336). Therefore, we systematically study the effect of the array density on the optical response of such systems, which could be later verified experimentally. We also investigate the manifestation of these findings in a hyperbolic-Fabry-Perot cell.

Polar liquids at charged interfaces: A dipolar shell theory.

The structure of polar liquids and electrolytic solutions, such as water and aqueous electrolytes, at interfaces underlies numerous phenomena in physics, chemistry, biology, and engineering. In this work, we develop a continuum theory that captures the essential features of dielectric screening by polar liquids at charged interfaces, including decaying spatial oscillations in charge and mass, starting from the molecular properties of the solvent. The theory predicts an anisotropic dielectric tensor of interfacial polar liquids previously studied in molecular dynamics simulations. We explore the effect of the interfacial polar liquid properties on the capacitance of the electrode/electrolyte interface and on hydration forces between two plane-parallel polarized surfaces. In the linear response approximation, we obtain simple formulas for the characteristic decay lengths of molecular and ionic profiles at the interface.

Electrotunable friction with ionic liquid lubricants.

Room-temperature ionic liquids and their mixtures with organic solvents as lubricants open a route to control lubricity at the nanoscale via electrical polarization of the sliding surfaces. Electronanotribology is an emerging field that has a potential to realize in situ control of friction-that is, turning the friction on and off on demand. However, fulfilling its promise needs more research. Here we provide an overview of this emerging research area, from its birth to the current state, reviewing the main achievements in non-equilibrium molecular dynamics simulations and experiments using atomic force microscopes and surface force apparatus. We also present a discussion of the challenges that need to be solved for future applications of electrotunable friction.

Conductive Metal-Organic Frameworks for Supercapacitors.

As a class of porous materials with crystal lattices, metal-organic frameworks (MOFs), featuring outstanding specific surface area, tunable functionality, and versatile structures, have attracted huge attention in the past two decades. Since the first conductive MOF is successfully synthesized in 2009, considerable progress has been achieved for the development of conductive MOFs, allowing their use in diverse applications for electrochemical energy storage. Among those applications, supercapacitors have received great interest because of their high power density, fast charging ability, and excellent cycling stability. Here, the efforts hitherto devoted to the synthesis and design of conductive MOFs and their auspicious capacitive performance are summarized. Using conductive MOFs as a unique platform medium, the electronic and molecular aspects of the energy storage mechanism in supercapacitors with MOF electrodes are discussed, highlighting the advantages and limitations to inspire new ideas for the development of conductive MOFs for supercapacitors.

Ionic liquids in conducting nanoslits: how important is the range of the screened electrostatic interactions?

Analytical models for capacitive energy storage in nanopores attract growing interest as they can provide in-depth analytical insights into charging mechanisms. So far, such approaches have been limited to models with nearest-neighbor interactions. This assumption is seemingly justified due to a strong screening of inter-ionic interactions in narrow conducting pores. However, how important is the extent of these interactions? Does it affect the energy storage and phase behavior of confined ionic liquids? Herein, we address these questions using a two-dimensional lattice model with next-nearest and further neighbor interactions developed to describe ionic liquids in conducting slit confinements. With simulations and analytical calculations, we find that next-nearest interactions enhance capacitance and stored energy densities and may considerably affect the phase behavior. In particular, in some range of voltages, we reveal the emergence of large-scale mesophases that have not been reported before but may play an important role in energy storage.

Structural Forces in Ionic Liquids: The Role of Ionic Size Asymmetry.

Ionic liquids (ILs) are charged fluids composed of anions and cations of different size and shape. The ordering of charge and density in ILs confined between charged interfaces underlies numerous applications of IL electrolytes. Here, we analyze the screening behavior and the resulting structural forces of a representative IL confined between two charge-varied plates. Using both molecular dynamics simulations and a continuum theory, we contrast the screening features of a more-realistic asymmetric system and a less-realistic symmetric one. The ionic size asymmetry plays a nontrivial role in charge screening, affecting both the ionic density profiles and the disjoining pressure distance dependence. Ionic systems with size asymmetry are stronger coupled systems, and this manifests itself both in their response to the electrode polarization and spontaneous structure formation at the interface. Analytical expressions for decay lengths of the disjoining pressure are obtained in agreement with the pressure profiles computed from molecular dynamics simulations.

Salt-in-Ionic-Liquid Electrolytes: Ion Network Formation and Negative Effective Charges of Alkali Metal Cations.

Salt-in-ionic liquid electrolytes have attracted significant attention as potential electrolytes for next generation batteries largely due to their safety enhancements over typical organic electrolytes. However, recent experimental and computational studies have shown that under certain conditions alkali cations can migrate in electric fields as if they carried a net negative effective charge. In particular, alkali cations were observed to have negative transference numbers at small mole fractions of alkali-metal salt that revert to the expected net positive transference numbers at large mole fractions. Simulations have provided some insights into these observations, where the formation of asymmetric ionic clusters, as well as a percolating ion network, could largely explain the anomalous transport of alkali cations. However, a thermodynamic theory that captures such phenomena has not been developed, as ionic associations were typically treated via the formation of ion pairs. The theory presented herein, based on the classical polymer theories, describes thermoreversible associations between alkali cations and anions, where the formation of large, asymmetric ionic clusters and a percolating ionic network are a natural result of the theory. Furthermore, we present several general methods to calculate the effective charge of alkali cations in ionic liquids. We note that the negative effective charge is a robust prediction with respect to the parameters of the theory and that the formation of a percolating ionic network leads to the restoration of net positive charges of the cations at large mole fractions of alkali metal salt. Overall, we find excellent qualitative agreement between our theory and molecular simulations in terms of ionic cluster statistics and the effective charges of the alkali cations.

Structural effects in nanotribology of nanoscale films of ionic liquids confined between metallic surfaces.

Room Temperature Ionic Liquids (RTILs) attract significant interest in nanotribology. However, their microscopic lubrication mechanism is still under debate. Here, using non-equilibrium molecular dynamics simulations, we investigate the lubrication performance of ultra-thin (<2 nm) films of [C2MIM]+ [NTf2]- confined between plane-parallel neutral surfaces of Au(111) or Au(100). We find that films consisting of tri-layers or bilayers, form ordered structures with a flat orientation of the imidazolium rings with respect to the gold surface plane. Tri-layers are unstable against loads >0.5 GPa, while bi-layers sustain pressures in the 1-2 GPa range. The compression of these films results in monolayers that can sustain loads of several GPa without significant loss in their lubrication performance. Surprisingly, in such ultra-thin films the imidazolium rings show higher orientational in-plane disorder, with and the rings adopting a tilted orientation with respect to the gold surface. The friction force and friction coefficient of the monolayers depends strongly on the structure of the gold plates, with the friction coefficient being four times higher for monolayers confined between Au(100) surfaces than for more compact Au(111) surfaces. We show that the general behaviour described here is independent of whether the metallic surfaces are modelled as polarizable or non-polarizable surfaces and speculate on the nature of this unexpected conclusion.