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Volume 195, 2016
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Uncertainty quantification for quantum chemical models of complex reaction networks

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Abstract

For the quantitative understanding of complex chemical reaction mechanisms, it is, in general, necessary to accurately determine the corresponding free energy surface and to solve the resulting continuous-time reaction rate equations for a continuous state space. For a general (complex) reaction network, it is computationally hard to fulfill these two requirements. However, it is possible to approximately address these challenges in a physically consistent way. On the one hand, it may be sufficient to consider approximate free energies if a reliable uncertainty measure can be provided. On the other hand, a highly resolved time evolution may not be necessary to still determine quantitative fluxes in a reaction network if one is interested in specific time scales. In this paper, we present discrete-time kinetic simulations in discrete state space taking free energy uncertainties into account. The method builds upon thermo-chemical data obtained from electronic structure calculations in a condensed-phase model. Our kinetic approach supports the analysis of general reaction networks spanning multiple time scales, which is here demonstrated for the example of the formose reaction. An important application of our approach is the detection of regions in a reaction network which require further investigation, given the uncertainties introduced by both approximate electronic structure methods and kinetic models. Such cases can then be studied in greater detail with more sophisticated first-principles calculations and kinetic simulations.

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Submitted
02 Jun 2016
Accepted
06 Jul 2016
First published
06 Jul 2016

This article is Open Access

Faraday Discuss., 2016,195, 497-520
Article type
Paper

Uncertainty quantification for quantum chemical models of complex reaction networks

J. Proppe, T. Husch, G. N. Simm and M. Reiher, Faraday Discuss., 2016, 195, 497
DOI: 10.1039/C6FD00144K

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