arXiv subjects

Benoit Coasne

Publications and source records attributed to Benoit Coasne.

11 recordsLinked to original sources

arXiv2026

Interplay of Structure and Dynamics in Solid Polymer Electrolytes: a Molecular Dynamics Study of LiPF6/polypropylene carbonate

Solid-state batteries (SSB) are emerging as next-generation electrochemical energy storage devices. Achieving high energy density in SSB relies on solid polymer electrolytes (SPE) that are electrochemically stable against both lithium metal and high-potential positive electrodes, two conditions that are difficult to satisfy without chemical degradation. In this work, molecular dynamics simulations are employed to investigate the relationship between structure and dynamics in carbonate-based SPE composed of polypropylene carbonate and lithium hexafluorophosphate (LiPF$_6$), at salt concentrations ranging from 0.32 to 1.21 mol$/$kg. Structural properties are analyzed under ambient pressure at the experimentally relevant temperature $T = 353$ K. Since the slow dynamical processes governing ion transport in these systems are inaccessible to direct molecular dynamics, transport properties are simulated at elevated temperatures up to 900 K and extrapolated to $T = 353$ K using Arrhenius behavior. The results reveal strong ionic correlations, a limited fraction of free ions, and a predominance of negatively charged clusters, especially at high salt concentration. At high temperature, the self-diffusion coefficient of Li$^+$ exceeds that of PF$_6^-$ due to weaker Li$^+$-carbonate and ion-ion interactions. However, at $T = 353$ K, Li$^+$ mobility becomes lower than that of the anion, consistent with typical experimental observations in SPE. As expected, the ionic conductivity $\sigma$ increases with temperature, while at $T = 353$ K it exhibits a maximum for salt concentrations between 1.0 and 1.1 mol$/$kg. Overall, the estimated physico-chemical parameters highlight the key role of ion correlations in SPE and suggest strategies to optimize electrolyte performance. The Arrhenius extrapolation approach used here provides valuable insight into ion transport mechanisms in solid polymer electrolytes.

cond-mat.soft↗

arXiv2026

Fluids at an electrostatically active surface: Optimum in interfacial friction and electrohydrodynamic drag

While fluids near a solid surface are at the core of applications in energy storage/conversion, electrochemistry/electrowetting and adsorption/catalysis, their nanoscale behavior remains only partially deciphered. Beyond conventional effects (e.g. adsorption/reaction, interfacial transport, phase transition shifts), recent experimental and theoretical studies on metallic surfaces have unraveled exotic peculiarities such as complex electrostatic screening, unexpected wetting transition, and interfacial quantum friction. These novel features require developing and embarking new tools to tackle the coupling between charge relaxation in the metal and molecular behavior in the vicinal fluid. Here, using the concept of Virtual Thomas-Fermi fluids, we employ a molecular simulation approach to investigate interfacial transport of fluid molecules and metal charge carriers at their interface--including the underlying electrostatically-driven dynamic friction and the coupling between charge current/hydrodynamic flow (the so-called electrohydrodynamic drag). While conventional numerical techniques consider either insulating materials or metallic materials described as polarizable, non-conducting media, our atom-scale strategy provides an effective yet realistic description of the solid excitation spectrum--including charge relaxation modes and conductivity. By applying this approach to water near metallic surfaces of various electrostatic screening lengths, we unveil a non-monotonous dependence of the fluid/solid friction on the metallicity with a maximum occurring as the charge dynamic structure factors of the solid and fluid strongly overlap. Moreover, we report a direct observation of the electrohydrodynamic drag which arises from the momentum transfer between the solid and liquid through dynamic electrostatic interactions and the underlying interfacial friction.

cond-mat.soft↗

arXiv2025

Hydrodynamic permeability of fluctuating porous membranes

In this paper we examine how porosity fluctuations affect the hydrodynamic permeability of a porous matrix or membrane. We introduce a fluctuating Darcy model, which couples the Navier-Stokes equation to the space- and time-dependent porosity fluctuations via a Darcy friction term. Using a perturbative approach, a Dyson equation for hydrodynamic fluctuations is derived and solved to express the permeability in terms of the matrix fluctuation spectrum. Surprisingly, the model reveals strong modifications of the fluid permeability in fluctuating matrices compared to static ones. Applications to various matrix excitation models - breathing matrix, phonons, active forcing - highlight the significant influence of matrix fluctuations on fluid transport, offering insights for optimizing membrane design for separation applications.

cond-mat.soft↗

arXiv2025

Intermittent molecular motion and first passage statistics for the NMR relaxation of confined water

The structure and dynamics of fluids confined in nanoporous media differ from those in bulk, which can be probed using NMR relaxation measurements. We here show, using atomistic molecular dynamics simulations of water in a slit nanopore, that the behavior of the NMR relaxation rate, R1, with varying surface interaction and confinement strength can be estimated from the exchange statistics of fluid molecules between the adsorbed surface layer and the bulk region, where molecules undergo intermittent dynamics. We employ first return passage time calculations to quantify the molecular exchange statistics, thereby linking microscopic parameters of the confined fluid-such as adsorption time, pore size, and diffusion coefficient-to the NMR relaxation rate. This approach allows to predict and interpret the molecular relaxation of fluids at interfaces using merely concepts of statistical mechanics and can be generalized to closed and open geometries.

cond-mat.soft↗

arXiv2024

Theory and Modeling of Transport for Simple Fluids in Nanoporous Materials: From Microscopic to Coarse-Grained Descriptions

We present the state-of-the-art theoretical modeling, molecular simulation, and coarse-graining strategies for the transport of gases and liquids in nanoporous materials (pore size 1-100 nm). Special emphasis is placed on the transport of small molecules in zeolites, active carbons, metal-organic frameworks, but also in nanoporous materials with larger pores such as ordered and disordered mesoporous oxides. We present different atomistic and mesoscopic methods as well as the theoretical formalisms. Attention is given to the investigation of different molecular transport coefficients - including the self, collective and transport diffusivities - but also to the determination of free energy barriers and their role in overall adsorption/separation process rates. We also introduce other available approaches such as hierarchical simulations and upscaling strategies. This review focuses on simple fluids in prototypical nanoporous materials. While the phenomena covered here capture the main physical mechanisms in such systems, complex molecules will exhibit additional specific features. For the sake of clarity and brevity, we also omit multicomponent systems (e.g. fluid mixtures, electrolytes, etc.) and electrokinetic effects arising when charged systems are considered (ionic species, charged surfaces, etc.), both of which add to the complexity.

cond-mat.soft↗

arXiv2024

Bridging Microscopic Dynamics and Hydraulic Permeability in Mechanically-Deformed Nanoporous Materials

In the field of nanoconfined fluids, there are striking examples of deformation/transport coupling in which mechanical solicitation of the confining host and dynamics of the confined fluid impact each other. While this intriguing behavior can be potentially used for practical applications (e.g. energy storage, phase separation, catalysis), the underlying mechanisms remain to be understood as they challenge existing frameworks. Here, using molecular simulations analyzed through concepts inherent to interfacial fluids, we investigate fluid flow in compliant nanoporous materials subjected to external mechanical stresses. We show that the pore mechanical properties significantly affect fluid flow as they lead to significant pore deformations and different density layering at the interface accounted for by invoking interfacial viscous effects. Despite such poromechanical effects, we show that the thermodynamic properties (i.e. adsorption) can be linked consistently to Darcy's law for the permeability by invoking a pore size definition based on the concept of Gibbs' dividing surface. In particular, regardless of the pore stiffness and applied external stress, all data can be rationalized by accounting for the fluid viscosity and slippage at the interface independent of a specific pore size definition. Using such a formalism, we establish that the intimate relation - derived using the linear response theory - between collective diffusivity and hydraulic permeability remains valid. This allows for linking consistently microscopic dynamics experiments and permeability experiments on fluid flow in compliant nanoporous materials.

physics.comp-ph↗

arXiv2023

On De Gennes Narrowing of Fluids Confined at the Molecular Scale in Nanoporous Materials

Beyond well-documented confinement and surface effects arising from the large internal surface and severely confining porosity of nanoporous hosts, the transport of nanoconfined fluids remains puzzling by many aspects. With striking examples such as memory, \textit{i.e.} non-viscous, effects, intermittent dynamics and surface barriers, the dynamics of fluids in nanoconfinement challenges classical formalisms (\textit{e.g.} random walk, viscous/advective transport) -- especially for molecular pore sizes. In this context, while molecular frameworks such as intermittent brownian motion, free volume theory and surface diffusion are available to describe the self-diffusion of a molecularly confined fluid, a microscopic theory for the collective diffusion (\textit{i.e.} permeability) -- which characterizes the flow induced by a thermodynamic gradient -- is lacking. Here, to fill this knowledge gap, we invoke the concept of `De Gennes narrowing' which relates the wavevector-dependent collective diffusivity $D_0(q)$ to the fluid structure factor $S(q)$. First, using molecular simulation for a simple yet representative fluid confined in a prototypical solid (zeolite), we unravel an essential coupling between the wavevector-dependent collective diffusivity and the structural ordering imposed on the fluid by the crystalline nanoporous host. Second, despite this complex interplay with marked Bragg peaks in the fluid structure, the fluid collective dynamics is shown to be accurately described through De Gennes narrowing. Moreover, in contrast to the bulk fluid, departure from De Gennes narrowing for the confined fluid in the macroscopic limit remains small as the fluid/solid interactions in severe confinement screen collective effects and, hence, weaken the wavevector dependence of collective transport.

physics.chem-ph↗

arXiv2022

Towards carbon neutral scientific societies: A case study with the International Adsorption Society

With increasing concerns over climate change, scientists must imperatively acknowledge their share in CO2 emissions. Considering the large emissions associated with scientific traveling - especially international conferences - initiatives to mitigate such impact are blooming. With the COVID-19 pandemic shattering our notion of private/professional interactions, the moment should be seized to reinvent science conferences and collaborations with a model respectful of the environment. Yet, despite efforts to reduce the footprint of conferences, there is a lack of a robust approach based on reliable numbers (emissions, carbon offsetting/removals, etc.) to accompany this shift of paradigm. Here, considering a representative scientific society, the International Adsorption Society, we report on a case study of the problem: making conferences carbon neutral while respecting the needs of scientists. We first provide a quantitative analysis of the CO2 emissions for the IAS conference in 2022 related to accommodation, catering, flights, etc. Second, we conduct two surveys probing our community view on the carbon footprint of our activities. These surveys mirror each other, and were distributed two years before and in the aftermath of our triennial conference (also corresponding to pre/post COVID times). By combining the different parts, we propose ambitious recommendations to shape the future of conferences.

physics.soc-ph↗

arXiv2020

Molecular origin of the reduced phase stability and faster formation/dissociation kinetics in confined methane hydrate

The microscopic mechanisms involved in the formation/dissociation of methane hydrate confined at the nanometer scale are unraveled using advanced molecular modeling techniques combined with a mesoscale thermodynamic approach. By means of atom-scale simulations probing coexistence upon confinement and free energy calculations, phase stability of confined methane hydrate is shown to be restricted to a narrower temperature and pressure domain than its bulk counterpart. The melting point depression at a given pressure, which is consistent with available experimental data, is shown to be quantitatively described using the Gibbs--Thomson formalism if used with accurate estimates for the pore/liquid and pore/hydrate surface tensions. The metastability barrier upon hydrate formation and dissociation is found to decrease upon confinement, therefore providing a molecular scale picture for the faster kinetics observed in experiments on confined gas hydrates. By considering different formation mechanisms -- bulk homogeneous nucleation, external surface nucleation, and confined nucleation within the porosity -- we identify a crossover in the nucleation process; the critical nucleus formed in the pore corresponds either to a hemispherical cap or a bridge nucleus depending on temperature, contact angle, and pore size. Using the classical nucleation theory, for both mechanisms, the typical induction time is shown to scale with the pore surface to volume ratio and, hence, the reciprocal pore size. These findings for the critical nucleus and nucleation rate associated to such complex transitions provide a mean to rationalize and predict methane hydrate formation in any porous media from simple thermodynamic data.

physics.chem-ph↗

arXiv2020

Electronic screening using a virtual Thomas-Fermi fluid for predicting wetting and phase transitions of ionic liquids at metal surfaces

Of relevance to energy storage, electrochemistry and catalysis, ionic and dipolar liquids display unexpected behaviours-especially in confinement. Beyond adsorption, over-screening and crowding effects, experiments have highlighted novel phenomena, such as unconventional screening and the impact of the electronic nature-metallic versus insulating - of the confining surface. Such behaviours, which challenge existing frameworks, highlight the need for tools to fully embrace the properties of confined liquids. Here we introduce a novel approach that involves electronic screening while capturing molecular aspects of interfacial fluids. Although available strategies consider perfect metal or insulator surfaces, we build on the Thomas-Fermi formalism to develop an effective approach that deals with any imperfect metal between these asymptotes. Our approach describes electrostatic interactions within the metal through a 'virtual' Thomas-Fermi fluid of charged particles, whose Debye length sets the screening length $\lambda$. We show that this method captures the electrostatic interaction decay and electrochemical behaviour on varying $\lambda$. By applying this strategy to an ionic liquid, we unveil a wetting transition on switching from insulating to metallic conditions.

physics.chem-ph↗

arXiv2020

Probing the concept of line tension down to the nanoscale

A novel mechanical approach is developed to explore by means of atom-scale simulation the concept of line tension at a solid-liquid-vapor contact line as well as its dependence on temperature, confinement, and solid/fluid interactions. More precisely, by estimating the stresses exerted along and normal to a straight contact line formed within a partially wet pore, the line tension can be estimated while avoiding the pitfalls inherent to the geometrical scaling methodology based on hemispherical drops. The line tension for Lennard-Jones fluids is found to follow a generic behavior with temperature and chemical potential effects that are all included in a simple contact angle parameterization. Former discrepancies between theoretical modeling and molecular simulation are resolved, and the line tension concept is shown to be robust down to molecular confinements. The same qualitative behavior is observed for water but the line tension at the wetting transition diverges or converges towards a finite value depending on the range of the solid/fluid interactions at play.

cond-mat.mes-hall↗