Journal
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
Volume 12, Issue 11, Pages 2954-2962Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acs.jpclett.1c00195
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Funding
- Midwest Integrated Center for Computational Materials (MICCoM) as part of the Computational Materials Sciences Program - U.S. Department of Energy, Office of Science, Basic Energy Sciences, Materials Sciences and Engineering Division, through Argonne Natio [DE-AC02-06CH11357]
- 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
- Villum Fonden, part of the Villum Center for the Science of Sustainable Fuels and Chemicals (V-SUSTAIN grant) [9455]
- US Department of Energy through the Computational Sciences Graduate Fellowship (DOE CSGF) [DE-FG0297ER25308]
- Office of Science of the U.S. Department of Energy [DE-AC02-05CH11231]
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This study utilizes neural networks to directly calculate the free energy surface of a prototypical heterogeneous catalysis reaction, uncovering the significant influence of surface atomic vibrational entropy on the reaction barrier. The findings demonstrate the importance of self-consistently identifying critical points on the FES for reactions involving considerable entropic effects.
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 that the 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.
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