• Medientyp: E-Artikel
  • Titel: Efficient global sensitivity analysis of kinetic Monte Carlo simulations using Cramérs–von Mises distance
  • Beteiligte: Dortaj, Sina; Matera, Sebastian
  • Erschienen: AIP Publishing, 2023
  • Erschienen in: The Journal of Chemical Physics, 159 (2023) 9
  • Sprache: Englisch
  • DOI: 10.1063/5.0160873
  • ISSN: 0021-9606; 1089-7690
  • Schlagwörter: Physical and Theoretical Chemistry ; General Physics and Astronomy
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  • Beschreibung: Typically, the parameters entering a physical simulation model carry some kind of uncertainty, e.g., due to the intrinsic approximations in a higher fidelity theory from which they have been obtained. Global sensitivity analysis (GSA) targets quantifying which parameter uncertainties impact the accuracy of the simulation results, e.g., to identify which parameters need to be determined more accurately. We present a GSA approach based on the Cramérs–von Mises distance. Unlike prevalent approaches, it combines the following properties: (i) it is equally suited for deterministic as well as stochastic model outputs, (ii) it does not require gradients, and (iii) it can be estimated from numerical quadrature without further numerical approximations. Using quasi-Monte Carlo for numerical integration and a first-principles kinetic Monte Carlo model for the CO oxidation on RuO2(110), we examine the performance of the approach. We find that the results agree very well with what is known in the literature about the sensitivity of this model and that the approach converges in a modest number of quadrature points. Furthermore, it appears to be robust against even extreme relative noise. All these properties make the method particularly suited for expensive (kinetic) Monte Carlo models because we can reduce the number of simulations as well as the target variance of each of these.