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吸附 - 解吸动力学中的硬动力学与软动力学:一维精确结果

Hard versus soft dynamics for adsorption-desorption kinetics: Exact results in one-dimension.

作者信息

Manzi S J, Huespe V J, Belardinelli R E, Pereyra V D

机构信息

Departamento de Física, Instituto de Física Aplicada (INFAP)-CONICET, Universidad Nacional de San Luis, Chacabuco 917, 5700 San Luis, Argentina.

出版信息

Phys Rev E Stat Nonlin Soft Matter Phys. 2009 Nov;80(5 Pt 1):051112. doi: 10.1103/PhysRevE.80.051112. Epub 2009 Nov 12.

Abstract

The adsorption-desorption kinetics is discussed in the framework of the kinetic lattice-gas model. The master equation formalism has been introduced to describe the evolution of the system, where the transition probabilities are written as an expansion of the occupation configurations of all neighboring sites. Since the detailed balance principle determines half of the coefficients that arise from the expansion, it is necessary to introduce ad hoc, a dynamic scheme to get the rest of them. Three schemes of the so-called hard dynamics, in which the probability of transition from single site cannot be factored into a part which depends only on the interaction energy and one that only depends on the field energy, and five schemes of the so-called soft dynamics, in which this factorization is possible, were introduced for this purpose. It is observed that for the hard dynamic schemes, the equilibrium and nonequilibrium observables, such as adsorption isotherms, sticking coefficients, and thermal desorption spectra, have a normal or physical sustainable behavior. While for the soft dynamics schemes, with the exception of the transition state theory, the equilibrium and nonequilibrium observables have several problems. Some of them can be regarded as abnormal behavior.

摘要

吸附 - 解吸动力学在动力学晶格气体模型的框架内进行讨论。引入了主方程形式来描述系统的演化,其中跃迁概率被写成所有相邻位点占据构型的展开式。由于细致平衡原理确定了展开式中出现的一半系数,因此有必要特别引入一种动力学方案来得到其余的系数。为此引入了三种所谓的硬动力学方案,其中从单个位点跃迁的概率不能分解为仅依赖于相互作用能的部分和仅依赖于场能的部分,以及五种所谓的软动力学方案,其中这种分解是可能的。据观察,对于硬动力学方案,平衡和非平衡可观测量,如吸附等温线、 sticking系数和热脱附谱,具有正常或物理上可持续的行为。而对于软动力学方案,除了过渡态理论外,平衡和非平衡可观测量存在几个问题。其中一些可被视为异常行为。

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