Entropy study of adsorption of H and O atoms on Ag(001) and Cu(001) surfaces, by means of DFT, Monte Carlo simulations and Cluster Approximation

IF 3.1 3区物理与天体物理 Q2 PHYSICS, MULTIDISCIPLINARY

Physica A: Statistical Mechanics and its Applications Pub Date : 2025-06-02 DOI:10.1016/j.physa.2025.130693

Elizabeth del V. Gómez , Fabricio O. Sanchez-Varretti , Lucía B. Avalle , Antonio J. Ramirez-Pastor , M. Cecilia Gimenez

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引用次数: 0

Abstract

DFT calculations are employed to calculate adsorption energies of hydrogen and oxygen atoms on Cu(001) and Ag(001) surfaces, in the presence of adsorbed neighboring atoms. These energies are used to carry out Monte Carlo (MC) simulations in the grand canonical ensemble. The thermodynamic process is monitored by following the dependence of the lattice coverage

θ

on the chemical potential

μ

(adsorption isotherm). Then, we perform the integration of

μ (θ)

over

θ

to calculate the configurational entropy per site of the adsorbed phase

s

as a function of the coverage. Based on the minima of the entropy function

s

, the most stable surface configurations are obtained and discussed in the framework of the lattice-gas theory. MC data are compared with theoretical results derived from Cluster Approximation (CA). CA is based on exact calculation of states on finite cells. From there, the thermodynamic properties can be obtained. A reasonable agreement is found for adsorption isotherms and entropy curves with both techniques (MC and CA). The comparison study supports the validity of the CA scheme to predict the behavior of a wide variety of adsorption systems.

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用DFT、蒙特卡罗模拟和聚类近似研究Ag（001）和Cu（001）表面H和O原子吸附的熵

采用DFT计算计算了在相邻原子被吸附的情况下，氢和氧原子在Cu（001）和Ag（001）表面上的吸附能。这些能量用于在大正则系综中进行蒙特卡罗（MC）模拟。通过观察晶格覆盖率θ与化学势μ（吸附等温线）的关系来监测热力学过程。然后，我们对μ(θ) / θ进行积分，以计算吸附相s的每个位点的构型熵作为覆盖率的函数。基于熵函数s的最小值，得到了最稳定的表面构型，并在晶格-气体理论的框架下进行了讨论。将MC数据与聚类近似（CA）的理论结果进行了比较。CA是基于有限单元上状态的精确计算。从这里，可以得到热力学性质。两种技术（MC和CA）所得的吸附等温线和熵曲线具有较好的一致性。对比研究支持了CA方案预测多种吸附体系行为的有效性。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

Physica A: Statistical Mechanics and its Applications 物理-物理：综合

CiteScore

7.20

自引率

9.10%

发文量

852

审稿时长

6.6 months

期刊介绍： Physica A: Statistical Mechanics and its Applications Recognized by the European Physical Society Physica A publishes research in the field of statistical mechanics and its applications. Statistical mechanics sets out to explain the behaviour of macroscopic systems by studying the statistical properties of their microscopic constituents. Applications of the techniques of statistical mechanics are widespread, and include: applications to physical systems such as solids, liquids and gases; applications to chemical and biological systems (colloids, interfaces, complex fluids, polymers and biopolymers, cell physics); and other interdisciplinary applications to for instance biological, economical and sociological systems.