A practical approach to the sensitivity analysis for kinetic Monte Carlo simulation of heterogeneous catalysis.
A practical approach to the sensitivity analysis for kinetic Monte Carlo simulation of heterogeneous catalysis.
复制标题
多相催化动力学蒙特卡罗模拟灵敏度分析的实用方法。
DOI：
10.1063/1.4974261
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发表时间：
2016
期刊：
影响因子：
--
通讯作者：
S. Matera
中科院分区：
文献类型：
--
作者：
M. Hoffmann;Felix Engelmann;S. Matera
晶格动力学蒙特卡罗模拟已经成为一个重要的工具，预测质量原子的理解复杂的表面化学反应动力学在广泛的反应条件。为了扩大它们的实际价值，在原子水平的催化体系的设计提供指导方针，这是非常可取的，容易评估一个给定的模型的灵敏度分析。这种敏感性分析的结果定量地表达了作为主要输出变量的周转频率对进入模型的速率常数的依赖性。在过去，敏感性分析的应用，如速率控制的程度，一直受到阻碍，其旺盛的计算工作所需的精确采样的数值衍生物的属性，是从随机模拟方法。在这项研究中，我们提出了一个有效的和强大的三阶段的方法，能够可靠地评估刚性微动力学模型的灵敏度措施，我们证明使用CO氧化RuO2（110）作为原型反应。在第一步中，我们利用Fisher信息矩阵过滤出的基本过程，只产生可忽略不计的敏感性。然后，我们采用基于线性响应理论的估计量来计算非临界条件下的敏感性测度，该估计量涵盖了大多数情况。最后，我们采用了一种方法来采样耦合有限差分评估的灵敏度措施的晶格为基础的模型。这使得即使在迄今难以控制的二阶相变附近的临界区域中也能够进行有效的评估。相结合的方法导致显着的计算节省直接的数值导数，并应有助于加速非均相催化剂的纳米级设计。
Lattice kinetic Monte Carlo simulations have become a vital tool for predictive quality atomistic understanding of complex surface chemical reaction kinetics over a wide range of reaction conditions. In order to expand their practical value in terms of giving guidelines for the atomic level design of catalytic systems, it is very desirable to readily evaluate a sensitivity analysis for a given model. The result of such a sensitivity analysis quantitatively expresses the dependency of the turnover frequency, being the main output variable, on the rate constants entering the model. In the past, the application of sensitivity analysis, such as degree of rate control, has been hampered by its exuberant computational effort required to accurately sample numerical derivatives of a property that is obtained from a stochastic simulation method. In this study, we present an efficient and robust three-stage approach that is capable of reliably evaluating the sensitivity measures for stiff microkinetic models as we demonstrate using the CO oxidation on RuO2(110) as a prototypical reaction. In the first step, we utilize the Fisher information matrix for filtering out elementary processes which only yield negligible sensitivity. Then we employ an estimator based on the linear response theory for calculating the sensitivity measure for non-critical conditions which covers the majority of cases. Finally, we adapt a method for sampling coupled finite differences for evaluating the sensitivity measure for lattice based models. This allows for an efficient evaluation even in critical regions near a second order phase transition that are hitherto difficult to control. The combined approach leads to significant computational savings over straightforward numerical derivatives and should aid in accelerating the nano-scale design of heterogeneous catalysts.
影响因子：
6.3
作者：
Hoffmann, Max J.;Matera, Sebastian;Reuter, Karsten
通讯作者：
Reuter, Karsten