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We build a model of transport of adsorbed fluid within the microporous network of kerogen's porosity, especially accounting for the adsorption-induced swelling exhibited by flexible kerogen structures. This model, based on Fujita-Kishimoto free volume theory that was historically developed for swellable polymers, is built over extensive results for the self-diffusion coefficients obtained by molecular dynamics calculations for a representative molecular model of kerogen designed to study the importance of flexibility effects on the properties of kerogen. To do so, we first highlight that transport within flexible kerogen incorporating the coupling between the dynamics of the fluid molecules and the kerogen matrix atoms does not introduce any significant collective effects in the usual long time limit. Then, we show that despite the slightly anisotropic diffusion properties, averaging over all the dimensions can still be performed in order to model the behavior of the transport properties with the amount of adsorbed fluid. Lastly, we link the increase of the self-diffusion coefficients and that of the accessible free volume with the fluid loading via the Fujita-Kishimoto model. We conclude by commenting on the evolution and significance of the model parameters over a broad range of thermophysical conditions.

Starting from the orthogonal dynamics of any given set of variables with respect to the projection variable used to derive the Mori–Zwanzig equation, a set of coupled Volterra equations is obtained that relate the projected time correlation functions between all the variables of interest. This set of equations can be solved using standard numerical inversion methods for Volterra equations, leading to a very convenient yet efficient strategy to obtain any projected time correlation function or contribution to the memory kernel entering a generalized Langevin equation. Using this strategy, the memory kernel related to the diffusion of tagged particles in a bulk Lennard–Jones fluid is investigated up to the long-term regime to show that the repulsive–attractive cross-contribution to memory effects represents a small but non-zero contribution to the self-diffusion coefficient.

We use path integral molecular dynamics simulations and theory to elucidate the interactions between charge carriers, as mediated by a lead halide perovskite lattice. We find that the charge-lattice coupling of MAPbI$_3$ results in a repulsive interaction between electrons and holes at intermediate distances. The effective interaction is understood using a Gaussian field theory, whereby the underlying soft, polar lattice contributes a nonlocal screening between quasiparticles. Path integral calculations of this nonlocal screening model are used to rationalize the small exciton binding energy and low radiative recombination rate observed experimentally and are compared to traditional Wannier-Mott and Fr\"ohlich models, which fail to do so. These results clarify the origin of the high power conversion efficiencies in lead halide perovskites. Emergent repulsive electron-hole interactions provide a design principle for optimizing soft, polar semiconductors., Comment: 7 pages, 2 figures, and SI

It has been recognized that the microporosity of shale organic matter, especially that of kerogen, strongly affects the hydrocarbon recovery process from unconventional reservoirs. So far, the numerical studies on hydrocarbon transport through the microporous phase of kerogen have neglected the effect of poromechanics, that is, the adsorption-induced deformations, by considering kerogen as a frozen, nondeformable, matrix. Here, we use molecular dynamics simulations to investigate methane diffusion in an immature (i.e., with high H/C ratio) kerogen matrix, while explicitly accounting for adsorption-induced swelling and internal matricial motions, covering both phonons and nonperiodic internal deformations. However, in the usual frozen matrix approximation, diffusivity decreases with increasing fluid loading, as evidenced by a loss of free volume, accounting for adsorption-induced swelling that gives rise to an increase in free volume and, hence, in diffusivity. The obtained trend is further rationalized using a Fujita-Kishimoto free volume theory initially developed in the context of diffusion in swelling polymers. We also quantify the enhancing effect of the matrix internal motions (i.e., at fixed volume) and show that it roughly gives an order of magnitude increase in diffusivity with respect to a frozen matrix, thanks to fluctuations in the pore connectivity. We eventually discuss the possible implications of this work to explain the productivity slowdown of hydrocarbon recovery from shale immature reservoirs.

© 2018 National Academy of Sciences. All Rights Reserved. Facile ionic transport in lead halide perovskites plays a critical role in device performance. Understanding the microscopic origins of high ionic conductivities has been complicated by indirect measurements and sample microstructural heterogeneities. Here, we report the direct visualization of halide anion interdiffusion in CsPbCl3–CsPbBr3 single crystalline perovskite nanowire heterojunctions using wide-field and confocal photoluminescence measurements. The combination of nanoscale imaging techniques with these single crystalline materials allows us to measure intrinsic anionic lattice diffusivities, free from complications of micro-scale inhomogeneity. Halide diffusivities were found to be between 10−13 and ∼10−12 cm2/second at about 100 °C, which are several orders of magnitudes lower than those reported in polycrystalline thin films. Spatially resolved photoluminescence lifetimes and surface potential measurements provide evidence of the central role of halide vacancies in facilitating ionic diffusion. Vacancy formation free energies computed from molecular simulation are small due to the easily deformable perovskite lattice, accounting for the high equilibrium vacancy concentration. Furthermore, molecular simulations suggest that ionic motion is facilitated by low-frequency lattice modes, resulting in low activation barriers for vacancy-mediated transport. This work elucidates the intrinsic solid-state ion diffusion mechanisms in this class of semisoft materials and offers guidelines for engineering materials with long-term stability in functional devices.

International audience; While hydrocarbon expulsion from kerogen is certainly the key step in shale oil/gas recovery, the poromechanical couplings governing this desorption process, taking place under a significant pressure gradient, are still poorly understood. Especially, most molecular simulation investigations of hydrocarbon adsorption and transport in kerogen have so far been performed under the rigid matrix approximation, implying that the pore space is independent of pressure, temperature, and fluid loading, or in other words, neglecting poromechanics. Here, using two hydrogenated porous carbon models as proxies for immature and overmature kerogen, that is, highly aliphatic hydrogen-rich vs highly aromatic hydrogen-poor models, we perform an extensive molecular-dynamics-based investigation of the evolution of the poroelastic properties of those matrices with respect to temperature, external pressure, and methane loading as a prototype alkane molecule. The rigid matrix approximation is shown to hold reasonably well for overmature kerogen even though accounting for flexibility has allowed us to observe the well-known small volume contraction at low fluid loading and temperature. Our results demonstrate that immature kerogen is highly deformable. Within the ranges of conditions considered in this work, its density can double and its accessible porosity (to a methane molecule) can increase from 0 to ∼30%. We also show that these deformations are significantly nonaffine (i.e., nonhomogeneous), especially upon fluid adsorption or desorption.

In a context of growing attention for shale gas, the precise impact of organic matter (kerogen) on hydrocarbon recovery from unconventional reservoirs still has to be assessed. Kerogen's microstructure is characterized by a very disordered pore network that greatly affects hydrocarbon transport. The specific structure and texture of this organic matter at the nanoscale is highly dependent on its origin. In this study, by the use of statistical physics and molecular dynamics, we shed some new lights on hydrocarbon transport through realistic molecular models of kerogen at different level of maturity [ Bousige et al. Nat. Mater. 2016 , 15 , 576 ]. Despite the apparent complexity, severe confinement effects controlled by the porosity of the various kerogens allow linear alkanes (from methane to dodecane) transport to be studied only via the self-diffusion coefficients of the species. The decrease of the transport coefficients with the amount of adsorbed fluid can be described by a free volume theory. Ultimately, the transport coefficients of hydrocarbons can be expressed simply as a function of the porosity (volume fraction of void) of the microstructure, thus paving the way for shale gas recovery predictions.

ACL; International audience; Facile ionic transport in lead halide perovskites plays a critical role in device performance. Understanding the microscopic origins of high ionic conductivities has been complicated by indirect measurements and sample microstructural heterogeneities. Here, we report the direct visualization of halide anion interdiffusion in CsPbCl3-CsPbBr3 single crystalline perovskite nanowire heterojunctions using wide-field and confocal photoluminescence measurements. The combination of nanoscale imaging techniques with these single crystalline materials allows us to measure intrinsic anionic lattice diffusivities, free from complications of micro-scale inhomogeneity. Halide diffusivities were found to be between 10(-13) and similar to 10(-12) cm(2)/second at about 100 degrees C, which are several orders of magnitudes lower than those reported in polycrystalline thin films. Spatially resolved photoluminescence lifetimes and surface potential measurements provide evidence of the central role of halide vacancies in facilitating ionic diffusion. Vacancy formation free energies computed from molecular simulation are small due to the easily deformable perovskite lattice, accounting for the high equilibrium vacancy concentration. Furthermore, molecular simulations suggest that ionic motion is facilitated by low-frequency lattice modes, resulting in low activation barriers for vacancy-mediated transport. This work elucidates the intrinsic solid-state ion diffusion mechanisms in this class of semisoft materials and offers guidelines for engineering materials with long-term stability in functional devices.

Accelerated reactive molecular dynamics simulations reveal the complex geological conversion path of organic matter into porous carbon (kerogen) and gas., The process by which organic matter decomposes deep underground to form petroleum and its underlying kerogen matrix has so far remained a no man’s land to theoreticians, largely because of the geological (Myears) timescale associated with the process. Using reactive molecular dynamics and an accelerated simulation framework, the replica exchange molecular dynamics method, we simulate the full transformation of cellulose into kerogen and its associated fluid phase under prevailing geological conditions. We observe in sequence the fragmentation of the cellulose crystal and production of water, the development of an unsaturated aliphatic macromolecular phase and its aromatization. The composition of the solid residue along the maturation pathway strictly follows what is observed for natural type III kerogen and for artificially matured samples under confined conditions. After expulsion of the fluid phase, the obtained microporous kerogen possesses the structure, texture, density, porosity and stiffness observed for mature type III kerogen and a microporous carbon obtained by saccharose pyrolysis at low temperature. As expected for this variety of precursor, the main resulting hydrocarbon is methane. The present work thus demonstrates that molecular simulations can now be used to assess, almost quantitatively, such complex chemical processes as petrogenesis in fossil reservoirs and, more generally, the possible conversion of any natural product into bio-sourced materials and/or fuel.

International audience; Despite recent focus on shale gas, hydrocarbon recovery from the ultraconfining and disordered porosity of organic matter in shales (kerogen) remains poorly understood. Key aspects such as the breakdown of hydrodynamics at the nanoscale and strong adsorption effects lead to unexplained non-Darcy behaviors. Here, molecular dynamics and statistical mechanics are used to elucidate hydrocarbon mixture transport through a realistic molecular model of kerogen [Bousige, C.; et al. Nat. Mater. 2016, 15, 576]. Owing to strong adsorption effects, velocity cross correlations between the mixture components and between molecules of the same species are shown to be negligible. This allows estimation of each component permeance from its self-diffusivity, which can be obtained from single-component data. These permeances are found to scale with the reciprocal of the alkane length and decrease with the number of adsorbed molecules following a simple free volume theory, therefore allowing mixture transport prediction as a function of the amount of trapped fluid.

International audience; This contribution presents a method for the numerical determination of the steady-state response of complex charged porous media to pressure, salt concentration and electric potential gradients. The Pore Network Model (PNM), describing the porosity as a network of pores connected by channels, is extended to capture electrokinetic couplings which arise at charged solid-liquid interfaces. This allows us to compute the macroscopic fluxes of solvent, salt and charge across a numerical sample submitted to macroscopic gradients. On the channel scale, the microscopic transport coefficients are obtained by solving analytically (in simple cases) or numerically the Poisson-Nernst-Planck and Stokes equations. The PNM approach then allows us to upscale these transport properties to the sample scale, accounting for the complex pore structure of the material via the distribution of channel diameters. The Onsager relations between macroscopic transport coefficients are preserved, as expected. However, electrokinetic couplings combined with the sample heterogeneity result for some macroscopic transport coefficients (e.g. permeability or electro-osmotic coefficient) in qualitative differences with respect to their microscopic counterparts. This underlines the care that should be taken when accounting for transport properties based on a single channel of average diameter.

International audience; Stochastic Rotation Dynamics (SRD) is a mesoscale simulation technique that captures hydrodynamic couplings in simple and complex fluids. It can be used in various hydrodynamic regimes and it is not restricted to specific geometries. We show here that SRD using the collisional coupling approach to capture momentum transfer between the semi-implicit solvent and the explicit counterions, is able to describe electro-kinetic effects, i.e. coupled electrostatic and hydrodynamic phenomena occurring at charged solid–liquid interfaces. The method is first validated for electro-osmosis in the simple case of a slit pore without added salt, for which an analytical solution of the Helmholtz–Smoluchowski theory is known, in a physical regime where this mean-field theory is valid. We then discuss the predictions of SRD for electro-osmosis beyond the range of validity of the Helmholtz–Smoluchowski (or Poisson–Nernst–Planck) theory, in particular due to ion–ion correlations at the surface, to charge localisation on discrete sites at the solid surface and to surface charge heterogeneity, that all contribute to a reduction of the electro-osmotic flow. In order to disentangle these last two aspects, we also investigate at the mean-field level a simple system with alternate charged and neutral stripes, using lattice-Boltzmann electro-kinetics simulations. Overall, this work opens new perspectives for the use of SRD as a generic mesoscopic simulation method for soft matter problems, in particular under confinement, since in practice many interfaces between fluids and solids are charged.

International audience; In porous media physics, calibrating model parameters through experiments is a challenge. This process is plagued with errors that come from modelling, measurement and computation of themacroscopic observables through random homogenization – the forward problem – as well as errors coming from the parameters fitting procedure – the inverse problem. In this work, we address these issues by considering a least-square formulation to identify parameters of the microscopic model on the basis on macroscopic observables. In particular, we discuss the selection of the macroscopic observableswhich we need to know in order to uniquely determine these parameters. To gain a better intuition andexplore the problem without a too high computational load, we mostly focus on the one-dimensionalcase. We show that the Newton algorithm can be efficiently used to robustly determine optimalparameters, even if some small statistical noise is present in the system.; En physique des milieux poreux, calibrer certains paramètres d’un modèle microscopique sur la base d’expériences donnant accès à des grandeurs macroscopiques est un enjeu majeur. Cette démarche est entachée d’erreurs de modèle, de mesure et de calculs dans la procédure d’homogénéisation : le problème direct est biaisé. La résolution du problème inverse, lorsqu’il s’agit d’estimer les paramètres à partir des observations, engendre aussi des erreurs. Nous considérons ici une formulation “moindres carrés” du problème, cherchant à minimiser l’erreur entre les quantités macroscopiques observées et celles calculées via l’homogénéisation aléatoire. Nous discutons en particulier de la nature des informations macroscopiques nécessaires pour déterminer de manière univoque les paramètres de la densité de probabilité des propriétés microscopiques. Afin d’explorer plus facilement cette question, nous nous intéressons ici essentiellement au cas unidimensionel. Nous montrons que le problème peut être résolu de manière efficace par l’algorithme de Newton, même en présence d’un petit bruit statistique.

As part of the disposal of nuclear waste in deep geological formations (Cigéo project), it is necessary to predict the flow of radionuclides in ionic form in charged porous media such as clays. The clay materials are complex and it is difficult to know their structure, especially at the nanoscale where electrokinetic phenomena become paramount. In this case, the strategy adopted in this work is to represent the porosity with a network of pores interconnected by channels. This requires to know the properties of the coupled transport at the channel scale taking into account the flow of solvent, solutes and charges under the influence of gradients of pressure, salt concentration and electrostatic potential. We used the Poisson-Nernst-Planck model to describe the electrokinetic transport in the channels. It can be shown that the behavior of these properties may vary between the channel scale and the sample scale (random networks constructed from parameters distributions). For example, it is found that the permeability of a network decreases as electrokinetic effects increase, which is not the case at the level of a single channel. These differences arise from the simultaneous presence of coupling between the flows and the heterogeneity of the sample. A numerical sample having the same properties as real clay sample has been created following a process of selection of the channels parameters, it has been used to conduct preliminary studies on clogging and desaturation in clay.; Dans le cadre du stockage des déchets nucléaires en couche géologique profonde (projet Cigéo), il est nécessaire de pouvoir prédire l'écoulement des radionucléides sous forme ionique dans des milieux poreux chargés tels que l'argile. Les matériaux argileux sont complexes et il est difficile de connaître leur structure, surtout à l'échelle nanoscopique où les phénomènes électrocinétiques deviennent primordiaux. Dans ce cas, la stratégie adoptée dans ce travail est de représenter la porosité à l'aide d'un réseau de pores connectés entre eux par des canaux. Cela nécessite de connaître les propriétés du transport couplé à l'échelle du canal en prenant en compte les flux de solvant, de solutés et de charges sous l'influence de gradients de pression, de concentration en sel et de potentiel électrostatique. La description du transport électrocinétique utilisée correspond à celle du modèle de Poisson-Nernst-Planck. On peut ainsi montrer que le comportement de ces propriétés peut différer entre l'échelle du canal et celle de l'échantillon (réseaux construits aléatoirement à partir de distributions de paramètres). Par exemple, on constate que la perméabilité d'un réseau diminue si les effets électrocinétiques augmentent, ce qui n'est pas le cas à l'échelle du canal. Ces différences proviennent de la présence simultanée de couplages entre les flux et de l'hétérogénéité du milieu. Un échantillon numérique ayant les mêmes propriétés qu'un échantillon réel d'argile a ainsi été créé au terme d'un processus de sélection des distributions de paramètres des canaux, il a ainsi servi à réaliser des études préliminaires sur le colmatage et la désaturation.

International audience; We introduce amethod for the numerical determination of the steady-state response of complex charged porous media to pressure, salt concentration, and electric potential gradients. The macroscopic fluxes of solvent, salt, and charge are computed within the framework of the Pore Network Model (PNM), which describes the pore structure of the samples as networks of pores connected to each other by channels. The PNM approach is used to capture the couplings between solvent and ionic flows which arise from the charge of the solid surfaces. For the microscopic transport coefficients on the channel scale, we take a simple analytical form obtained previously by solving the Poisson-Nernst-Planck and Stokes equations in a cylindrical channel. These transport coefficients are upscaled for a given network by imposing conservation laws for each pores, in the presence of macroscopic gradients across the sample. The complex pore structure of the material is captured by the distribution of channel diameters. We investigate the combined effects of this complex geometry, the surface charge, and the salt concentration on the macroscopic transport coefficients. The upscaled numerical model preserves the Onsager relations between the latter, as expected. The calculated macroscopic coefficients behave qualitatively as their microscopic counterparts, except for the permeability and the electro-osmotic coupling coefficient when the electrokinetic effects are strong. Quantitatively, the electrokinetic couplings increase the difference between the macroscopic coefficients and the corresponding ones for a single channel of average diameter.

International audience; We report the calculation of all the transfer coefficients which couple the solvent and ionic fluxes through a charged pore under the effect of pressure, electrostatic potential, and concentration gradients. We use a combination of analytical calculations at the Poisson-Nernst-Planck and Navier-Stokes levels of description and mesoscopic lattice simulations based on kinetic theory. In the absence of added salt, i.e., when the only ions present in the fluid are the counterions compensating the charge of the surface, exact analytical expressions for the fluxes in cylindrical pores allow us to validate a new lattice-Boltzmann electrokinetics (LBE) scheme which accounts for the osmotic contribution to the transport of all species. The influence of simulation parameters on the numerical accuracy is thoroughly investigated. In the presence of an added salt, we assess the range of validity of approximate expressions of the fluxes computed from the linearized Poisson-Boltzmann equation by a systematic comparison with LBE simulations.