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Trade-Off between Accuracy and Universality in Linear Energy Relations for Alcohol Dehydrogenation on Transition Metals

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journal contribution
posted on 11.06.2015, 00:00 by Jérémie Zaffran, Carine Michel, Françoise Delbecq, Philippe Sautet
To screen heterogeneous catalysts in silico, the linear energy relationships derived from the Brønsted–Evans–Polanyi principle are extremely useful. They connect the reaction energy of a given elementary step to its activation energy, hence providing data that can be fed to kinetics models at a minimal cost. However, to ensure reasonable predictions, it is essential to control the statistical error intrinsic to this approach. We derived several types of linear energy relations for a series of CH and OH bond scissions in simple alcohol molecules on compact facets of seven transition metals (Co, Ni, Ru, Rh, Pd, Ir, and Pt) aiming at a single but accurate relation. The quality of the relation depends on its nature and/or on the manner the data are split: a single linear relation can be constructed for all metals together on the basis of the original Brønsted–Evans–Polanyi formulation with a mean absolute error smaller than 0.1 eV, whereas the more recent transition state scaling approach requires considering each metal individually to reach an equivalent accuracy. In addition, a close statistical analysis demonstrates that errors stemming from such predictive models are not uniform along the set of metals and of chemical reactions that is considered opening the road to a better control of error propagation.