Olivier Politano

Electrochemical properties of crystallized dilithium squarate: insight from dispersion-corrected density functional theory

The stacking parameters, lattice constants, and bond lengths of solvent-free dilithium squarate (Li(2)C(4)O(4)) crystals were investigated using density functional theory with and without dispersion corrections. The shortcoming of the GGA (PBE) calculation with respect to the dispersive forces appears in the form of an overestimation of the unit cell volume up to 5.8%. The original Grimme method for dispersion corrections has been tested together with modified versions of this scheme by changing the damping function. One of the modified dispersion-corrected DFT schemes, related to a rescaling of van der Waals radii, provides significant improvements for the description of intermolecular interactions in Li(2)C(4)O(4) crystals: the predicted unit cell volume lies then within 0.9% from experimental data. We applied this optimised approach to the screening of hypothetical framework structures for the delithiated (LiC(4)O(4)) and lithiated (Li(3)C(4)O(4)) phases, i.e. oxidized and reduced squarate forms. Their relative energies have been analysed in terms of dispersion and electrostatic contributions. The most stable phases among the hypothetical models for a given lithiation rate were selected in order to calculate the corresponding average voltages (either upon lithiation or delithiation of Li(2)C(4)O(4)). A first step towards energy partitioning in view of interpretating crystal phases relative stability in link with (de)-intercalation processes has been performed through the explicit evaluation of electrostatic components of lattice energy from atomic charges gained with the Atoms in Molecules (AIM) method.

A 3D mesoscopic approach for discrete dislocation dynamics

In recent years a noticeable renewed interest in modeling dislocations at the mesoscopic scale has been developed leading to significant advances in the field. This interest has arisen from a desire to link the atomistic and macroscopic length scales. In this context, we have recently developed a 3D-discrete dislocation dynamics model (DDD) based on a nodal discretization of the dislocations. We present here the basis of our DDD model and two examples of studies with single and multiple slip planes.

Formation of surface roughness on nanocrystalline aluminium samples under straining by molecular dynamics studies

The surface roughening of nanocrystalline aluminium samples was investigated by molecular dynamics simulations. Attention was focused on the fact that roughness increases with the grain size and the strain. The elastic–plastic transition was found at around 3.5% strain and a reverse Hall–Petch effect was observed under straining conditions. Then, different strain distributions in grains and grain boundaries at the sample surface were highlighted, yielding to the formation of local roughness. Finally, a linear relationship between the magnitude of roughness and the out-of-plane strain component was found.

Theoretical and numerical considerations on the surface energy for deformed isotropic nanocrystals

In this paper we start by presenting an analytical analysis to determine the variation in the surface energy of isotropic solids when they are deformed in the elastic domain. This part of our work was based on a recent formulation proposed by Sanfeld and Steinchen and modified for the case of pure solids. We continue our presentation by deducing the form of the surface energy variation by means of molecular dynamics simulations at a finite temperature (300 K). These simulations were performed with single nanocrystals of Al and deformed in the elastic regime along one direction parallel to the surface. These simulations also allowed us to determine the variation in the interplanar spacing of the atomic layers near the surface. Our simulations for the (100), (110) and (111) surfaces exhibit the same multilayer relaxation tendency obtained by other numerical and experimental results.

A Reactive Force Field Molecular Dynamics Simulation Study of Corrosion of Nickel

The interaction of water molecules on a nickel surface was studied using ReaxFF (reactive force field) molecular dynamics. This approach was originally developed by van Duin et al. to study the hydrocarbon chemistry and the catalytic properties of organic compounds. To our knowledge, this method has not been used to study the corrosion processes of nickel exposed to water, which is what we set out to achieve in the present investigation. To do so, calculations were first performed using ReaxFF in order to reproduce certain well-known properties of pure nickel and nickel-water systems. This allowed us to study the adsorption of a single water molecule interacting with an optimized nickel surface. We also investigated the interaction of 405 molecules of water (ρ=0.99 g.cm-3) on the (100), (110) and (111) surfaces of a single crystal of nickel at 300 K. The results show that a water bilayer is adsorbed on nickel surfaces: the first water layer is directly bonded to the surface, whereas the molecules in the first and second layers are held together by hydrogen bonds.

Numerical Determination of Intrinsic Diffusion Coefficient of Aluminide Coatings on Metals

This paper presents a numerical method to determine the composition dependent diffusivities and to predict the concentration profile during the interdiffusion process. The intrinsic diffusion coefficients in diffusion aluminide coatings (Fe-Al) were determined at 1000oC. The obtained diffusion coefficient for iron in Fe3Al or FeAl is in the range 10-10 to 10-9 cm2.s-1. The aluminum diffusion coefficient varies from 10-11 to 10-7 cm2.s-1 in the same phases.The present approach also permits to model the reactive diffusion in the Fe-Al systems.

On the dynamics of dislocation patterning

Recent computer simulations on dislocation patterning have provided remarkable results in accordance with empirical laws. Moreover, several analytical models on dislocation dynamics have provided qualitative insight on dislocation patterning. However, a model, based on partial differential equations, which gives a dynamical evolution of dislocation patterns in function of measurable variables still missing. Here, we give a re-formulation of a model proposed some years ago. From this formulation, we obtained that the onset of a dislocation instability is related to the applied stress. The analytical and numerical results reported are partial and studies on this direction are under development.

Electronic structure and energy decomposition analyses as a tool to interpret the redox potential ranking of naphtho-, biphenyl- and biphenylene-quinone isomers

By calling on modelling approaches we have performed a comparative study on the redox properties of various naphtho-, biphenyl- and biphenylene-quinone isomers. These different compounds exhibit as a whole a redox potential range between 2.09 and 2.90 V vs. Li+/Li. A specific methodology was used to decrypt the interplay among isomerism, aromaticity and antiaromaticity modifications and the stabilization/destabilization effects due to other molecular components on this key electrochemical feature for electrode materials of batteries. In particular, energy decomposition analysis, within the Quantum Theory of Atoms in Molecules, along with the electron and electron spin population changes upon reduction nicely rationalise the observed potential trends. While 1,2- and 2,3-isomers show the highest/lowest redox potential in the biphenylene-quinone series, a reverse trend is observed for the naphtho-quinone, the compound having the two carbonyl groups on distinct rings being characterized by an intermediate value in both cases. There is instead almost no differentiation between 1,2 and 2,3 isomers for the biphenyl-quinone family.

Study of the Reactive Dynamics of Nanometric Metallic Multilayers Using Molecular Dynamics : The Al-Ni System

A molecular dynamics study of a layered Ni-Al-Ni system is developed using an embedded atom method potential. The specific geometry is designed to model a Ni-Al nanometric metallic multilayer. The system is initially thermalized at the fixed temperature of 600 K. We first observe the interdiffusion of Ni and Al at the interfaces, which is followed by the spontaneous phase formation of B2-NiAl in the Al layer. The solid-state reaction is associated with a rapid systems heating which further enhances the diffusion processes. NiAl phase is organized in small regions separated by grain boundaries. This study confirms the hypothesis of a layer-by-layer development of the new phase. For longer times, the temperature is notably higher (> 1000 K) and the system may partly lose some its B2-NiAl microstructure in favor of the formation of Ni3Al in L12 configuration. This work shows the spontaneous development of a real exothermic solid-state reaction in metallic nanosystems mostly constituted by interfaces.

Numerical Simulations on the Growth of Thin Oxide Films on Aluminum Substrates

We investigated the oxidation of nanocrystalline aluminum surfaces by using variable charge molecular dynamics at 600 K under three oxygen pressures: 1, 10 and 20 atm. The interaction potential was described by the electrostatic plus (Es+) model that allows dynamical charge transfer among atoms. We mainly focused on the effect of the oxygen pressure on the oxidation kinetic, the chemical composition and the microstructure of the oxide films formed. The results show that oxidation kinetics as well as chemical composition and microstructure depend on the applied oxygen pressure. The oxide film thickness tends to a limiting value equal to ~3 nm. Finally, we obtained a partially crystalline oxide films for all oxygen pressures and we observed that the degree of crystallinity increases with time.