Journal ArticleDOI
Addressing global uncertainty and sensitivity in first-principles based microkinetic models by an adaptive sparse grid approach.
Sandra Döpking,Craig P. Plaisance,D. Strobusch,Karsten Reuter,Christoph Scheurer,Sebastian Matera +5 more
Reads0
Chats0
TLDR
This work addresses the propagation of sizable errors from the use of approximate Density Functional Theory to the catalytic turnover frequency (TOF) by global sensitivity and uncertainty analysis and opens the way for a global sensitivity analysis of more complex models, for instance, models based on kinetic Monte Carlo simulations.Abstract:
In the last decade, first-principles-based microkinetic modeling has been developed into an important tool for a mechanistic understanding of heterogeneous catalysis. A commonly known, but hitherto barely analyzed issue in this kind of modeling is the presence of sizable errors from the use of approximate Density Functional Theory (DFT). We here address the propagation of these errors to the catalytic turnover frequency (TOF) by global sensitivity and uncertainty analysis. Both analyses require the numerical quadrature of high-dimensional integrals. To achieve this efficiently, we utilize and extend an adaptive sparse grid approach and exploit the confinement of the strongly non-linear behavior of the TOF to local regions of the parameter space. We demonstrate the methodology on a model of the oxygen evolution reaction at the Co3O4 (110)-A surface, using a maximum entropy error model that imposes nothing but reasonable bounds on the errors. For this setting, the DFT errors lead to an absolute uncertainty of several orders of magnitude in the TOF. We nevertheless find that it is still possible to draw conclusions from such uncertain models about the atomistic aspects controlling the reactivity. A comparison with derivative-based local sensitivity analysis instead reveals that this more established approach provides incomplete information. Since the adaptive sparse grids allow for the evaluation of the integrals with only a modest number of function evaluations, this approach opens the way for a global sensitivity analysis of more complex models, for instance, models based on kinetic Monte Carlo simulations.read more
Citations
More filters
Journal Article
First-principles calculations of electronic structure and spectra of strongly correlated systems: the LDA+U method
TL;DR: In this paper, a generalization of the Local Density Approximation (LDA) method for the systems with strong Coulomb correlations is presented which gives a correct description of the Mott insulators.
Journal ArticleDOI
First-principles-based multiscale modelling of heterogeneous catalysis
TL;DR: First-principles-based multiscale models are ever more successful in addressing the wide range of length and time scales over which material-function relationships evolve in heterogeneous catalysis as mentioned in this paper.
Journal ArticleDOI
Progress in Accurate Chemical Kinetic Modeling, Simulations, and Parameter Estimation for Heterogeneous Catalysis
TL;DR: Current trends and future areas of advancement in chemical kinetic modeling, simulation, and parameter estimation are described: ranging from elementary step calculations to multiscale modeling to the role of advanced statistical methods for incorporating uncertainties in predictions.
Journal ArticleDOI
Systematic Enumeration of Elementary Reaction Steps in Surface Catalysis
TL;DR: This work presents a systematic method for enumerating all intermediates and elementary reactions relevant to a chemical process of interest and constructs reaction networks for C,H,O-containing systems consisting of up to four non-hydrogen atoms (more than 1 million reactions).
Journal ArticleDOI
A Bayesian framework for adsorption energy prediction on bimetallic alloy catalysts
Osman Mamun,Osman Mamun,Kirsten T. Winther,Kirsten T. Winther,Jacob R. Boes,Jacob R. Boes,Thomas Bligaard,Thomas Bligaard +7 more
TL;DR: This article extends the single descriptor linear scaling relation to a multi-descriptor linear regression models to leverage the correlation between adsorption energy of any two pair of adsorbates and proposes an ad hoc Bayesian Model Averaging approach to make a robust prediction.
References
More filters
Journal ArticleDOI
Solar Water Splitting Cells
Michael G. Walter,Emily L. Warren,James R. McKone,Shannon W. Boettcher,Qixi Mi,Elizabeth A. Santori,Nathan S. Lewis +6 more
TL;DR: The biggest challenge is whether or not the goals need to be met to fully utilize solar energy for the global energy demand can be met in a costeffective way on the terawatt scale.
Journal ArticleDOI
Density-functional theory and strong interactions: Orbital ordering in Mott-Hubbard insulators
TL;DR: In this article, it was shown that electronic orbital ordering is a necessary condition to obtain the correct crystal structure and parameters of the exchange interaction for the Mott-Hubbard insulator.
Journal ArticleDOI
First-principles calculations of the electronic structure and spectra of strongly correlated systems: the LDA+ U method
TL;DR: In this paper, a generalization of the Local Density Approximation (LDA) method for the systems with strong Coulomb correlations is presented which gives a correct description of the Mott insulators.
Journal ArticleDOI
Towards the computational design of solid catalysts
TL;DR: The first steps towards using computational methods to design new catalysts are reviewed and how, in the future, such methods may be used to engineer the electronic structure of the active surface by changing its composition and structure are discussed.
Journal ArticleDOI
Insights into Current Limitations of Density Functional Theory
TL;DR: This work characterized and understood the delocalization error and static correlation error of commonly used approximations of density functional theory through the perspective of fractional charges and fractional spins introduced recently.