Statistical Surface Thermodynamics

Patrykiejew, A.; Sokołowski, Stefan; Pizio, Orest

doi:10.1002/9783527680580.ch46

Cited by 15 publications

(12 citation statements)

References 751 publications

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“…Therefore, all aspects related to chemisorption and catalytic processes at surfaces are not considered" as discussed on p. 883 of Ref. 55. In the current setting specifically adsorbed species forming covalent bonds or exchanging charge with the surface need to be treated as reactant, as discussed in Sec.…”

Section: Classical Continuum/electronic Gc-dft For Electrocatalytic Systemsmentioning

confidence: 99%

Grand-Canonical Approach to Density Functional Theory of Electrocatalytic Systems: Thermodynamics of Solid-Liquid Interfaces at Constant Ion and Electrode Potentials

Melander

Kuisma²,

Christensen³

et al. 2018

Preprint

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Properties of solid-liquid interfaces are of immense importance for electrocatalytic and electrochemical systems but modelling such interfaces at the atomic level presents a serious challenge and approaches beyond standard methodologies are needed. An atomistic computational scheme needs treat at least part of the system quantum mechanically to include adsorption and reactions while the entire system is in thermal equilibrium. The experimentally relevant macroscopic control variables are temperature, electrode potential, choice of the solvent and ions and these need to be explicitly included in the computational model as well; this calls for an thermodynamic ensemble with fixed ion and electrode potentials. In this work a general framework within density functional theory with fixed electron and ion chemical potentials in the grand canonical ensemble is established for modelling electrocatalytic and electrochemical interfaces. Starting from a fully quantum mechanical description of nuclei and electrons, a systematic coarse-graining is employed to establish various computational schemes including i) the combination of classical and electronic density functional theories within the grand canonical ensemble and ii) on the simplest level a chemically and physically sound way to obtain the (modified) Poisson-Boltzmann (mPB) implicit solvent model. The detailed and rigorous derivation clearly establishes which approximations are needed for coarse-graining as well as highlights which details and interactions are omitted in vein of computational feasibility. The transparent approximations also allow removing some the constraints and coarse-graining if needed. We implement various mPB models in the GPAW code and test their capabilities to model capacitance of electrochemical interfaces as well as study different approaches for modelling partly periodic charged systems. Our rigorous and well-defined DFT coarse-graining scheme to continuum electrolytes highlights the inadequacy of current linear dielectric models for treating properties of the electrochemical interface.<br><br>

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Section: Classical Continuum/electronic Gc-dft For Electrocatalytic Systemsmentioning

confidence: 99%

Grand-Canonical Approach to Density Functional Theory of Electrocatalytic Systems: Thermodynamics of Solid-Liquid Interfaces at Constant Ion and Electrode Potentials

Melander

Kuisma²,

Christensen³

et al. 2018

Preprint

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“…The formation of multilayer adsorbed films on solid substrates and wetting phenomena have been studied for several decades, both experimentally, with different theoretical approaches, and computer simulation methods. A comprehensive description of the results can be found in many books and review articles [ 1 , 2 , 3 , 4 , 5 , 6 , 7 , 8 , 9 ]. Among the most frequently used theoretical models of adsorption are various lattice gas models [ 3 , 8 , 10 , 11 , 12 , 13 , 14 , 14 ].…”

Section: Introductionmentioning

confidence: 99%

Lattice Model of Multilayer Adsorption of Particles with Orientation Dependent Interactions at Solid Surfaces

Patrykiejew

2021

Molecules

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A simple lattice model has been used to study the formation of multilayer films by fluids with orientation-dependent interactions on solid surfaces. The particles, composed of two halves (A and B) were allowed to take on one of six different orientations. The interaction between a pair of differently oriented neighboring particles was assumed to depend on the degrees to which their A and B parts overlap. Here, we have assumed that the AA interaction was strongly attractive, the AB interaction was set to zero, while the BB interaction was varied between 0 and −1.0. The ground state properties of the model have been determined for the systems being in contact with non-selective and selective walls over the entire range of BB interaction energies between 0 and −1.0. It has been demonstrated that the structure of multilayer films depends on the strengths of surface potential felt by differently oriented particles and the interaction between the B halves of fluid particles. Finite temperature behavior has been studied by Monte Carlo simulation methods. It has been shown that the bulk phase phase diagram is qualitatively independent of the BB interaction energy, and has the swan neck shape, since the high stability of the dense ordered phase suppresses the possibility of the formation of disordered liquid-like phase. Only one class of non-uniform systems with the BB interaction set to zero has been considered. The results have been found to be consistent with the predictions stemming form the ground state considerations. In particular, we have found that a complete wetting occurs at any temperature, down to zero. Furthermore, the sequences of layering transitions, and the structure of multilayer films, have been found to be the same as observed in the ground state.

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“…Here, we should mention that various lattice models (Ising, Potts, etc.) are commonly used to describe the behavior of diverse physical systems [ 18 , 19 ].…”

Section: Introductionmentioning

confidence: 99%

Phase Transitions in Two-Dimensional Systems of Janus-like Particles on a Triangular Lattice

Patrykiejew

2021

IJMS

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We studied the phase behavior of two-dimensional systems of Janus-like particles on a triangular lattice using Monte Carlo methods. The model assumes that each particle can take on one of the six orientations with respect to the lattice, and the interactions between neighboring particles were weighted depending on the degree to which their A and B halves overlap. In this work, we assumed that the AA interaction was fixed and attractive, while the AB and BB interactions varied.We demonstrated that the phase behavior of the systems considered strongly depended on the magnitude of the interaction energies between the AB and BB halves. Here, we considered systems with non-repulsive interactions only and determined phase diagrams for several systems. We demonstrated that the phase diagram topology depends on the temperature at which the close-packed systems undergo the orientational order–disorder transition.

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Statistical Surface Thermodynamics

Cited by 15 publications

References 751 publications

Grand-Canonical Approach to Density Functional Theory of Electrocatalytic Systems: Thermodynamics of Solid-Liquid Interfaces at Constant Ion and Electrode Potentials

Grand-Canonical Approach to Density Functional Theory of Electrocatalytic Systems: Thermodynamics of Solid-Liquid Interfaces at Constant Ion and Electrode Potentials

Lattice Model of Multilayer Adsorption of Particles with Orientation Dependent Interactions at Solid Surfaces

Phase Transitions in Two-Dimensional Systems of Janus-like Particles on a Triangular Lattice

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