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nitrogen_dissociation_ChemArXiv_v2.pdf (2.43 MB)

Neural Network Sampling of the Free Energy Landscape for Nitrogen Dissociation on Ruthenium

revised on 03.03.2021, 19:30 and posted on 04.03.2021, 08:46 by Elizabeth Lee, Thomas Ludwig, Boyuan Yu, Aayush Singh, François Gygi, Jens Kehlet Nørskov, Juan de Pablo

In heterogeneous catalysis, free energy profiles of reactions govern the mechanisms, rates, and equilibria. Energetics are conventionally computed using the harmonic approximation (HA), which requires determination of critical states a priori. Here, we use neural networks to efficiently sample and directly calculate the free energy surface (FES) of a prototypical heterogeneous catalysis reaction—the dissociation of molecular nitrogen on ruthenium—at density functional theory-level accuracy. We find vibrational entropy of surface atoms, often neglected in HA for transition metal catalysts, contributes significantly to the reaction barrier. The minimum free energy path for dissociation reveals an “on-top” adsorbed molecular state prior to the transition state. While a previously reported flat-lying molecular metastable state can be identified in the potential energy surface, it is absent in the FES at relevant reaction temperatures. These findings demonstrate the importance of identifying critical points self-consistently on the FES for reactions that involve considerable entropic effects.


Midwest Integrated Center for Computational Materials (MICCoM) as part of the Computational Materials Sciences Program funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences, Materials Sciences and Engineering Division, through Argonne National Laboratory, under Contract No. DE-AC02-06CH11357

Villum Fonden, part of the Villum Center for the Science of Sustainable Fuels and Chemicals (V-SUSTAIN grant 9455)


Advanced Scientific Computing Research

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SUNCAT Center for Interface Science and Catalysis as part of the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Chemical Sciences, Geosciences, and Biosciences Division, Catalysis Science Program


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University of Chicago


United States

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Declaration of Conflict of Interest

no conflict of interest