蒙特卡罗方法
动力学蒙特卡罗方法
统计物理学
灵敏度(控制系统)
动能
动态蒙特卡罗方法
蒙特卡罗分子模拟
反应速率
限制
计算机科学
化学
物理
数学
经典力学
统计
工程类
马尔科夫蒙特卡洛
催化作用
机械工程
生物化学
电子工程
作者
Hakim Meskine,Sebastian Matera,Matthias Scheffler,Karsten Reuter,Horia Metiu
出处
期刊:Surface Science
[Elsevier]
日期:2009-06-01
卷期号:603 (10-12): 1724-1730
被引量:98
标识
DOI:10.1016/j.susc.2008.08.036
摘要
The conceptual idea of degree of rate control (DRC) approaches is to identify the "rate limiting step" in a complex reaction network by evaluating how the overall rate of product formation changes when a small change is made in one of the kinetic parameters. We examine two definitions of this concept by applying it to first-principles kinetic Monte Carlo simulations of the CO oxidation at RuO2(1 1 0). Instead of studying experimental data we examine simulations, because in them we know the surface structure, reaction mechanism, the rate constants, the coverage of the surface and the turn-over frequency at steady-state. We can test whether the insights provided by the DRC are in agreement with the results of the simulations thus avoiding the uncertainties inherent in a comparison with experiment. We find that the information provided by using the DRC is non-trivial: It could not have been obtained from the knowledge of the reaction mechanism and of the magnitude of the rate constants alone. For the simulations the DRC provides furthermore guidance as to which aspects of the reaction mechanism should be treated accurately and which can be studied by less accurate and more efficient methods. We therefore conclude that a sensitivity analysis based on the DRC is a useful tool for understanding the propagation of errors from the electronic structure calculations to the statistical simulations in first-principles kinetic Monte Carlo simulations.
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