Assessing the Performance of Exchange‐Correlation Density Functionals in Describing the Iron‐Catalyzed Ammonia Synthesis System

Smith, Evangelos [Univ. of Wisconsin, Madison, WI (United States)]; Figueras‐Valls, Marc [Univ. of Wisconsin, Madison, WI (United States)]; Mavrikakis, Manos [Univ. of Wisconsin, Madison, WI (United States)] (ORCID:0000000252935356)

doi:10.1002/ceur.202500030

DOE OSTI · 3012736

Assessing the Performance of Exchange‐Correlation Density Functionals in Describing the Iron‐Catalyzed Ammonia Synthesis System

Smith, Evangelos [Univ. of Wisconsin, Madison, WI (United States)]·Figueras‐Valls, Marc [Univ. of Wisconsin, Madison, WI (United States)]·Mavrikakis, Manos [Univ. of Wisconsin, Madison, WI (United States)] (ORCID:0000000252935356)

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Abstract

Density functional theory (DFT) has been widely employed for elucidating mechanistic aspects of heterogeneous catalysis. However, the accuracy of DFT calculations relies heavily on selecting an exchange-correlation (XC) functional that correctly describes the electronic structure of materials involved in the reactions. This study assesses the accuracy of several XC density functionals for modeling the iron-catalyzed ammonia synthesis system. In the assessment of functional accuracy, experimental references are compared to DFT-calculated values for the formation energy of gas-phase ammonia and nitrogen, bulk Fe/Fe-nitride (γ′-Fe 4 N) lattice constants and cohesive/formation energies, and nitrogen and ammonia binding energies on Fe(100), Fe(111), Fe(110), and γ′-Fe 4 N(111). It is observed that the experimental value for each of these descriptors is accurately modeled by at least one functional. RPBE alone provides reliable estimates for both the lattice constant and cohesive energy of Fe and γ′-Fe 4 N. Temperature-programmed desorption experiments led to estimates for N and NH 3 adsorption across several Fe-based facets that are best captured by RPBE. These results highlight the importance of choosing an appropriate XC functional that accurately describes experimental systems and offer insights into effectively modeling the interactions between nitrogen and ammonia on Fe-based surfaces.

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Smith, Evangelos [Univ. of Wisconsin, Madison, WI (United States)], Figueras‐Valls, Marc [Univ. of Wisconsin, Madison, WI (United States)], Mavrikakis, Manos [Univ. of Wisconsin, Madison, WI (United States)] (ORCID:0000000252935356). 2025-07-09. Assessing the Performance of Exchange‐Correlation Density Functionals in Describing the Iron‐Catalyzed Ammonia Synthesis System. https://doi.org/10.1002/ceur.202500030

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