scholarly journals Electrostatic interactions between ions near Thomas–Fermi substrates and the surface energy of ionic crystals at imperfect metals

2017 ◽  
Vol 199 ◽  
pp. 129-158 ◽  
Author(s):  
V. Kaiser ◽  
J. Comtet ◽  
A. Niguès ◽  
A. Siria ◽  
B. Coasne ◽  
...  
Keyword(s):  
Surface Energy ◽  
Electrostatic Interactions ◽  
Electrostatic Energy ◽  
Screening Length ◽  
Thomas Fermi ◽  
Electronic Screening ◽  
Ionic Systems ◽  
Metallic Wall ◽  
Electrostatic Contribution ◽  
Dimensional Crystal

The electrostatic interaction between two charged particles is strongly modified in the vicinity of a metal. This situation is usually accounted for by the celebrated image charges approach, which was further extended to account for the electronic screening properties of the metal at the level of the Thomas–Fermi description. In this paper we build upon a previous approach [M. A. Vorotyntsev and A. A. Kornyshev, Zh. Eksp. Teor. Fiz., 1980, 78(3), 1008–1019] and successive works to calculate the 1-body and 2-body electrostatic energy of ions near a metal in terms of the Thomas–Fermi screening length. We propose workable approximations suitable for molecular simulations of ionic systems close to metallic walls. Furthermore, we use this framework to calculate analytically the electrostatic contribution to the surface energy of a one dimensional crystal at a metallic wall and its dependence on the Thomas–Fermi screening length. These calculations provide a simple interpretation for the surface energy in terms of image charges, which allows for an estimation of the interfacial properties in more complex situations of a disordered ionic liquid close to a metal surface. The counter-intuitive outcome is that electronic screening, as characterized by a molecular Thomas–Fermi length lTF, profoundly affects the wetting of ionic systems close to a metal, in line with the recent experimental observation of capillary freezing of ionic liquids in metallic confinement.

scholarly journals Wetting transition of ionic liquids at metal surfaces: A computational molecular approach to electronic screening using a virtual Thomas-Fermi fluid

2020 ◽  
Author(s):  
Alexander Schlaich ◽  
Dongliang Jin ◽  
Lyderic Bocquet ◽  
Benoit Coasne
Keyword(s):  
Ionic Liquids ◽  
Energy Storage ◽  
Electrostatic Interactions ◽  
Debye Length ◽  
Wetting Transition ◽  
Molecular Fluids ◽  
Thomas Fermi ◽  
Electronic Screening ◽  
Novel Approach ◽  
The Impact

Abstract Of particular relevance to energy storage, electrochemistry and catalysis, ionic and dipolar liquids display a wealth of unexpected fundamental behaviors – in particular in confinement. Beyond now well-documented adsorption, overscreening and crowding effects1,2,3, recent experiments have highlighted novel phenomena such as unconventional screening4 and the impact of the electronic nature – metallic versus insulating – of the confining surface on wetting/phase transitions5,6. Such behaviors, which challenge existing theoretical and numerical modeling frameworks, point to the need for new powerful tools to embrace the properties of confined ionic/dipolar liquids. Here, we introduce a novel atom-scale approach which allows for a versatile description of electronic screening while capturing all molecular aspects inherent to molecular fluids in nanoconfined/interfacial environments. While state of the art molecular simulation strategies only consider perfect metal or insulator surfaces, we build on the Thomas-Fermi formalism for electronic screening to develop an effective approach that allows dealing with any imperfect metal between these asymptotes. The core of our approach is to describe electrostatic interactions within the metal through the behavior of a `virtual' Thomas-Fermi fluid of charged particles, whose Debye length sets the Thomas-Fermi screening length λ in the metal. This easy-to-implement molecular method captures the electrostatic interaction decay upon varying λ from insulator to perfect metal conditions, while describing very accurately the capacitance behavior – and hence the electrochemical properties – of the metallic confining medium. By applying this strategy to a nanoconfined ionic liquid, we demonstrate an unprecedented wetting transition upon switching the confining medium from insulating to metallic. This novel approach provides a powerful framework to predict the unsual behavior of ionic liquids, in particular inside nanoporous metallic structures, with direct applications for energy storage and electrochemistry.

scholarly journals Phase Behavior of Melts of Diblock-Copolymers with One Charged Block

Polymers ◽  
2019 ◽  
Vol 11 (6) ◽  
pp. 1027 ◽  
Author(s):  
Alexey A. Gavrilov ◽  
Alexander V. Chertovich ◽  
Igor I. Potemkin
Keyword(s):  
Phase Diagram ◽  
Phase Behavior ◽  
Electrostatic Interactions ◽  
Diblock Copolymers ◽  
Volume Fraction ◽  
Microphase Separation ◽  
Dissipative Particle Dynamics ◽  
Homogeneous Structure ◽  
Electrostatic Energy ◽  
Ordered Structures

In this work, we investigated the phase behavior of melts of block-copolymers with one charged block by means of dissipative particle dynamics with explicit electrostatic interactions. We assumed that all the Flory–Huggins χ parameters were equal to 0. We showed that the charge- correlation attraction solely can cause microphase separation with a long-range order; a phase diagram was constructed by varying the volume fraction of the uncharged block and the electrostatic interaction parameter λ (dimensionless Bjerrum length). The obtained phase diagram was compared to the phase diagram of “equivalent” neutral diblock-copolymers with the non-zero χ-parameter between the beads of different blocks. The neutral copolymers were constructed by grafting the counterions to the corresponding co-ions of the charged block with further switching off the electrostatic interactions. Surprisingly, the differences between these phase diagrams are rather subtle; the same phases in the same order are observed, and the positions of the order-disorder transition ODT points are similar if the λ-parameter is considered as an “effective” χ-parameter. Next, we studied the position of the ODT for lamellar structure depending on the chain length N. It turned out that while for the uncharged diblock copolymer the product χcrN was almost independent of N, for the diblock copolymers with one charged block we observed a significant increase in λcrN upon increasing N. This can be attributed to the fact that the counterion entropy prevents the formation of ordered structures, and its influence is more pronounced for longer chains since they undergo the transition to ordered structures at smaller values of λ, when the electrostatic energy becomes comparable to kbT. This was supported by studying the ODT in diblock-copolymers with charged blocks and counterions cross-linked to the charged monomer units. The ODT for such systems was observed at significantly lower values of λ, with the difference being more pronounced at longer chain lengths N. The fact that the microphase separation is observed even at zero Flory–Huggins parameter can be used for the creation of “high-χ” copolymers: The incorporation of charged groups (for example, ionic liquids) can significantly increase the segregation strength. The diffusion of counterions in the obtained ordered structures was studied and compared to the case of a system with the same number of charged groups but a homogeneous structure; the diffusion coefficient along the lamellar plane was found to be higher than in any direction in the homogeneous structure.

scholarly journals An accurate single descriptor for ion–π interactions

2020 ◽  
Vol 7 (6) ◽  
pp. 1036-1045 ◽  
Author(s):  
Zhangyun Liu ◽  
Zheng Chen ◽  
Jinyang Xi ◽  
Xin Xu
Keyword(s):  
Electrostatic Interactions ◽  
Quantitative Description ◽  
Physical Nature ◽  
Binding Energies ◽  
Electrostatic Energy ◽  
Π Interactions ◽  
Practical Strategy ◽  
Leading Term ◽  
Level Method ◽  
High Level

Abstract Non-covalent interactions between ions and π systems play an important role in molecular recognition, catalysis and biology. To guide the screen and design for artificial hosts, catalysts and drug delivery, understanding the physical nature of ion–π complexes via descriptors is indispensable. However, even with multiple descriptors that contain the leading term of electrostatic and polarized interactions, the quantitative description for the binding energies (BEs) of ion–π complexes is still lacking because of the intrinsic shortcomings of the commonly used descriptors. Here, we have shown that the impartment of orbital details into the electrostatic energy (coined as OEE) makes an excellent single descriptor for BEs of not only spherical, but also multiply-shaped, ion–π systems, highlighting the importance of an accurate description of the electrostatic interactions. Our results have further demonstrated that OEEs from a low-level method could be calibrated to BEs from a high-level method, offering a powerful practical strategy for an accurate prediction of a set of ion–π interactions.

Thomas-Fermi model of electronic screening in semiconductor nanocrystals

2006 ◽  
Vol 74 (3) ◽  
pp. 519-525 ◽  
Author(s):  
D Ninno ◽  
F Trani ◽  
G Cantele ◽  
K. J Hameeuw ◽  
G Iadonisi ◽  
...  
Keyword(s):  
Semiconductor Nanocrystals ◽  
Fermi Model ◽  
Thomas Fermi ◽  
Electronic Screening

Deformation of metallic liquid drop by electric field for contacts in molecular–organic electronics

2009 ◽  
Vol 465 (2106) ◽  
pp. 1799-1808 ◽  
Author(s):  
M. Bag ◽  
D. Gupta ◽  
N. Arun ◽  
K.S. Narayan
Keyword(s):  
Solid State ◽  
Surface Energy ◽  
Electric Field ◽  
Linear Response ◽  
Liquid Drop ◽  
Electrostatic Energy ◽  
Critical Voltage ◽  
Metallic Liquid ◽  
Linear Response Regime ◽  
Polymer Electronics

We study and use the behaviour of a metallic liquid drop in the presence of an external electric field (EF). The droplet profile is governed by the stabilizing surface energy and the destabilizing electrostatic energy, with a critical voltage beyond which the droplet becomes unstable. We explore the EF-induced behaviour of low melting temperature alloy in the liquid state and observe that the droplet modifications in the linear response regime can be retained upon cooling the drop to the solid state. We demonstrate that this procedure can be used as an electrode with precise dimensions for applications in molecular and polymer electronics.

Electrostatic Contribution of the Proteoglycans to the In-Plane Shear and Compressive Stiffness of Corneal Stroma

2010 ◽  
Author(s):  
Hamed Hatami-Marbini ◽  
Peter M. Pinsky
Keyword(s):  
Extracellular Matrix ◽  
Articular Cartilage ◽  
Electrostatic Interactions ◽  
Corneal Stroma ◽  
Collagen Fibers ◽  
Connective Tissues ◽  
Compressive Stiffness ◽  
Electrostatic Contribution ◽  
Repulsive Forces

The extracellular matrix (ECM) is a fibrous structure embedded in an aqueous gel. The mechanical and electrostatic interactions of the ECM constituents, i.e. collagen fibers and proteoglycans (PGs), define the structure and mechanical response of connective tissues (CTs) such as cornea and articular cartilage. Proteoglycans are complex macromolecules consisting of linear chains of repeating gylcosaminoglycans (GAGs) which are covalently attached to a core protein. PGs can be as simple as decorin with a single GAG side chain or as complex as aggrecan with many GAGs. Decorin is the simplest small leucine-rich PG and is the main PG inside the corneal stroma. It has an arch shape and links non-covalently at its concave surface to the collagen fibrils. It has been shown that while collagen fibers inside the extracellular matrix resist the tensile forces, the negatively charged glycosaminoglycans and their interaction with water give compressive stiffness to the tissue. The role of PGs in biomechanical properties of the connective tissues has mainly been studied in order to explore the behavior of articular cartilage [1], which is a CT with large and highly negatively charged PGs, aggrecans. In order to explain the role of PGs in this tissue, it is commonly assumed that their contribution to the CT elasticity is because of both the repulsive forces between negatively charged GAGs and GAG interactions with free mobile charges in the ionic bath. The electrostatic contribution to the shear and compressive stiffness of cartilage is modeled by approximating GAGs as charged rods [1]. The Poisson-Boltzmann equation is used to compute the change in electrical potential and mobile ion distributions which are caused by the macroscopic deformation.

Electrostatic Potential Energy in Protein-Drug Complexes

2021 ◽  
Vol 28 ◽  
Author(s):  
Gabriela Bitencourt-Ferreira ◽  
Walter Filgueira de Azevedo Junior
Keyword(s):  
Potential Energy ◽  
Binding Affinity ◽  
Electrostatic Interactions ◽  
Computational Models ◽  
Scoring Function ◽  
Predictive Performance ◽  
Electrostatic Energy ◽  
Protein Drug ◽  
Scoring Functions ◽  
Semi Empirical

Background: Electrostatic interactions are one of the forces guiding the binding of molecules to proteins. The assessment of this interaction through computational approaches makes it possible to evaluate the energy of protein-drug complexes. Objective: Our purpose here is to review some the of methods used to calculate the electrostatic energy of protein-drug complexes and explore the capacity of these approaches for the generation of new computational tools for drug discovery using the abstraction of scoring function space. Method: Here we present an overview of AutoDock4 semi-empirical scoring function used to calculate binding affinity for protein-drug complexes. We focus our attention on electrostatic interactions and how to explore recently published results to increase the predictive performance of the computational models to estimate the energetics of protein-drug interactions. Public data available at Binding MOAD, BindingDB, and PDBbind were used to review the predictive performance of different approaches to predict binding affinity. Results: A comprehensive outline of the scoring function used to evaluate potential energy available in docking programs is presented. Recent developments of computational models to predict protein-drug energetics were able to create targeted-scoring functions to predict binding to these proteins. These targeted models outperform classical scoring functions and highlight the importance of electrostatic interactions in the definition of the binding. Conclusion: Here, we reviewed the development of scoring functions to predict binding affinity through the application of a semi-empirical free energy scoring function. Our studies show the superior predictive performance of machine learning models when compared with classical scoring functions and the importance of electrostatic interactions for binding affinity.

Dynamics and Transport of Molecules in Polymer and Colloidal-Rod Networks

2007 ◽  
Vol 1060 ◽  
Author(s):  
Kyongok Kang
Keyword(s):  
Electric Field ◽  
Electrostatic Interactions ◽  
Polymer Network ◽  
Mesh Size ◽  
Limited Range ◽  
Correlation Spectroscopy ◽  
Relaxation Dynamics ◽  
Screening Length ◽  
Cholesteric Phase ◽  
Hydrodynamic Screening

ABSTRACTRe-orientational dynamics of liquid crystal molecules in a polymer network subjected to an electric field is studied by means of light diffraction [1]. When the optical pitch of the electric-field induced cholesteric phase is small compared to the optical wavelength of light, dynamic light scattering (DLS) can be performed to extract the relaxation dynamics of the chiral nematic molecules in the presence of the polymer network. Intriguingly, the reactive mesogenic type of polymer network exhibits a confinement effect, which can be probed within the limited range of scattering angles that comply with the structural correlation length in the system [2].Diffusive mass transport of molecules through a rod network can be studied via fluorescence correlation spectroscopy (FCS) and DLS. Long time self-diffusion of tracer spheres (silica and proteins) in isotropic and nematic colloidal-rod networks (fd-viruses) is systematically studied for various tracer-sphere sizes as compared to the mesh size of the network [3]. In addition, by varying the salt concentration, the relative contribution of electrostatic interactions can be varied. A theory is developed where the diffusion coefficient is expressed in terms of the hydrodynamic screening length of the highly entangled rod-network. The hydrodynamic screening length of rod networks is extracted from diffusion data as a function of the rod concentration both for isotropic and nematic networks [4-5].

Experimental and Numerical Studies on B-DNA Overstretching Transition in Presence of Sodium Ions at Physiological Temperature

2007 ◽  
Vol 121-123 ◽  
pp. 1093-1096 ◽  
Author(s):  
Hong Xia Fu ◽  
Chan Ghee Koh ◽  
Hu Chen ◽  
Chwee Teck Lim
Keyword(s):  
Optical Tweezers ◽  
Electrostatic Interactions ◽  
Electrostatic Energy ◽  
Stacking Interactions ◽  
Base Stacking ◽  
Physiological Temperature ◽  
Dna Molecule ◽  
Metropolis Monte Carlo ◽  
Dna Double Helix ◽  
Transition Force

In this paper, the effects of Na+ concentration on the overstretching transition of B-DNA molecule at physiological temperature are studied by both experimental and numerical methods. Using optical tweezers, the relationship of external force and relative extension is obtained by stretching single B-DNA molecule at 37°C. As the concentration increases from 0.909mM to 909mM, the overstretching transition force increases from 65.65 ± 1.2pN to 43.07 ± 1.2pN. An analytical expression is derived, which shows that overstretching transition force is linear with the natural logarithm of salt concentration. Based on a previous model, a three-dimensional model is proposed herein and solved by Metropolis Monte Carlo method. The bending deformation of DNA backbones, cooperativity of base-stacking interactions, electrostatic interactions, and spatial effects of DNA double helix structure are taken into account. Our key contribution is that the electrostatic energy is explicitly given as a function of folding angle and Na+ concentration. A new parameter is also introduced to account for the cooperativity of base-stacking interactions. The numerical results of this model are in good agreement with our experimental results.

Calculations of electrostatic interactions in biological systems and in solutions

1984 ◽  
Vol 17 (3) ◽  
pp. 283-422 ◽  
Author(s):  
Arieh Warshel ◽  
Stephen T. Russell
Keyword(s):  
Electrostatic Interactions ◽  
Structural Information ◽  
Van Der Waals ◽  
Effective Radius ◽  
Biological Molecules ◽  
Electrostatic Energy ◽  
Energy Correlation ◽  
Polar Solvents ◽  
Charged Amino Acids ◽  
The Given

Correlating the structure and action of biological molecules requires knowledge of the corresponding relation between structure and energy. Probably the most important factors in such a structure– energy correlation are associated with electrostatic interactions. Thus the key requirement for quantative understanding of the action of biological molecules is the ability to correlate electrostatic interactions with structural information. To appreciate this point it is useful to compare the electrostatic energy of a charged amino acid in a polar solvent to the corresponding van der Waals energy. The electrostatic free energy, ΔGel, can be approximated (as will be shown in Section II) by the Born formula (ΔGel = –(166Q2/ā) (I – I/E)). Where ΔGel is given in kcal/mol, Qis the charge of the given group, in units of electron charge, āis the effective radius of the group, and E is the dielectric constant of the solvent. With an effective radius of charged amino acids of approximately 2 Å, Born's formula gives about – 80 kcal/mol for their energy in polar solvents where E is larger than 10. This energy is two orders of magnitude larger than the van der Waals interaction of such groups and their surroundings.

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