Search results for " canonical"
showing 10 items of 58 documents
A New Monte Carlo Method for the Titration of Molecules and Minerals
2007
The charge state of molecules and solid/liquid interfaces is of paramount importance in the understanding of the reactivity and the physico-chemical properties of many systems. In this work, we porpose a new Monte Carlo method in the grand canonical ensemble using the primitive model, which allows us to simulate the titration behavior of macromolecules or solids at constant pH. The method is applied to the charging process of colloidal silica particles dispersed in a sodium salt solution for various concentrations and calcium silicate hydrate nano-particles in a calcium hydroxide solution. An excellent agreement is found between the experimental and simulated results.
Coadsorption of NRR and HER Intermediates Determines the Performance of Ru-N4 toward Electrocatalytic N2 Reduction
2021
Efficiency of the electrochemical N2 reduction reaction (NRR) to ammonia is seriously limited by the competing hydrogen evolution reaction (HER) but our current atomic-scale insight on the factors controlling HER/NRR competition are unknown. Herein we unveil the elementary mechanism, thermodynamics, and kinetics determining the HER/NRR selectivity on the state-of-the-art NRR electrocatalyst, Ru-N4 using constant potential density functional theory calculations (DFT). The calculations show that NRR and HER intermediates coadsorb on the catalyst where HER is greatly suppressed by the NRR intermediates. The first reaction step leading to either *NNH or *H determines the selectivity towards NRR…
Analysis and assessment of trace element contamination in offshore sediments of the Augusta Bay (SE Sicily): A multivariate statistical approach base…
2014
Abstract An application of multivariate statistical methods is provided to identify anthropogenic contaminants and lithogenic elements in offshore sediments collected near the heavily industrialized Augusta Bay, Sicily. An exploratory statistical technique, based on canonical correlation analysis (CCA) and mixture density estimation approach, is used for distinguishing between natural and anthropogenic contributions of trace elements in the investigated sediments. Following the intensive industrialization of Augusta area, marine sediments reveal the severe impact of local anthropogenic activities for many elements (e.g. As, Cd, Hg, Pb, and Sb), which are considered very dangerous for the en…
The action of the unitary group associated with a quadratic extension of fields
1999
Given a quadratic extension L/k of fields of characteristic different from 2 and a unitary space (V, f) of finite dimension over L, we give a representation, as simple as possible, of the form which f induces by restriction on a k-substructure of V. This, in turn, allows one to study the orbits of the unitary group U(V, f) in the set of k-substructures of V of a given dimension.
Molecular Selectivity of CH 4 –C 2 H 6 Mixed Hydrates: A GCMC Study
2021
International audience; In this paper, we report the first grand canonical Monte Carlo simulation study aiming at characterizing the competitive trapping of CH4 and C2H6 molecules into clathrate hydrates under temperature conditions typical of those encountered at the surface of Titan. Various compositions of the fluid in contact with the clathrate phase have been considered in the simulations, including pure methane, pure ethane, and mixed fluids made of various methane/ethane ratios. The trapping isotherms obtained from the simulations clearly show that ethane molecules can be enclathrated at lower pressures than methane molecules. In addition, they provide evidence that the methane molec…
Grand Canonical Monte Carlo Simulations to Determine the Optimal Interlayer Distance of a Graphene Slit-Shaped Pore for Adsorption of Methane, Hydrog…
2021
The adsorption—for separation, storage and transportation—of methane, hydrogen and their mixture is important for a sustainable energy consumption in present-day society. Graphene derivatives have proven to be very promising for such an application, yet for a good design a better understanding of the optimal pore size is needed. In this work, grand canonical Monte Carlo simulations, employing Improved Lennard–Jones potentials, are performed to determine the ideal interlayer distance for a slit-shaped graphene pore in a large pressure range. A detailed study of the adsorption behavior of methane, hydrogen and their equimolar mixture in different sizes of graphene pores is obtained through ca…
Grand-canonical approach to density functional theory of electrocatalytic systems: Thermodynamics of solid-liquid interfaces at constant ion and elec…
2018
Properties of solid-liquid interfaces are of immense importance for electrocatalytic and electrochemical systems, but modeling such interfaces at the atomic level presents a serious challenge and approaches beyond standard methodologies are needed. An atomistic computational scheme needs to treat at least part of the system quantum mechanically to describe adsorption and reactions, while the entire system is in thermal equilibrium. The experimentally relevant macroscopic control variables are temperature, electrode potential, and the choice of the solvent and ions, and these need to be explicitly included in the computational model as well; this calls for a thermodynamic ensemble with fixed…
Simulation and theory of fluid demixing and interfacial tension of mixtures of colloids and nonideal polymers.
2005
An extension of the Asakura-Oosawa-Vrij model of hard sphere colloids and non-adsorbing polymers, that takes polymer non-ideality into account through a repulsive stepfunction pair potential between polymers, is studied with grand canonical Monte Carlo simulations and density functional theory. Simulation results validate previous theoretical findings for the shift of the bulk fluid demixing binodal upon increasing strength of polymer-polymer repulsion, promoting the tendency to mix. For increasing strength of the polymer-polymer repulsion, simulation and theory consistently predict the interfacial tension of the free colloidal liquid-gas interface to decrease significantly for fixed colloi…
Unmixing of Polymer Blends Confined in Ultrathin Films: Crossover between Two-Dimensional and Three-Dimensional Behavior
2006
The interplay between chain conformations and phase separation in binary symmetric polymer mixtures confined into thin films by "neutral" hard walls (i.e., walls that do not preferentially attract or repel one of the two components of the mixture) is studied by Monte Carlo simulations. Using the bond fluctuation model on a simple cubic lattice in the semi grand canonical ensemble, we locate the critical temperature of demixing via finite size scaling methods for a wide range of chain lengths (16/= N/= 256 effective monomers per chain) and film thicknesses (2/= D/= 19 lattice spacings). Simultaneously, we investigate the geometrical structure of the chains, showing that despite using melt de…
Why are there no comprehensively digital scholarly editions of classical texts?
2018
Currently, no 'canonical' classical text with a multi-testimonial tradition has a digital scholarly edition based on a complete digital transcription of all primary sources, and on the automated collation of those transcriptions. Most classicists simply do not feel that they need such editions. I argue that this is ultimately due to the 'canonization' of the corpus of classical texts. Classicists are more focussed on the 'Text' than on the documents (manuscripts) and their texts: they tend not to consider the textual variance in the manuscripts as culturally meaningful in itself, but merely instrumental in view of the constitutio textus. I suspect that we will not have 'comprehensively digi…