Assessing Exchange-Correlation Functionals for Heterogeneous Catalysis of Nitrogen Species.

Increasing interest in the sustainable synthesis of ammonia, nitrates, and urea has led to an increase in studies of catalytic conversion between nitrogen-containing compounds using heterogeneous catalysts. Density functional theory (DFT) is commonly employed to obtain molecular-scale insight into these reactions, but there have been relatively few assessments of the exchange-correlation functionals that are best suited for heterogeneous catalysis of nitrogen compounds. Here, we assess a range of functionals ranging from the generalized gradient approximation (GGA) to the random phase approximation (RPA) for the formation energies of gas-phase nitrogen species, the lattice constants of representative solids from several common classes of catalysts (metals, oxides, and metal-organic frameworks (MOFs)), and the adsorption energies of a range of nitrogen-containing intermediates on these materials. The results reveal that the choice of exchange-correlation functional and van der Waals correction can have a surprisingly large effect and that increasing the level of theory does not always improve the accuracy for nitrogen-containing compounds. This suggests that the selection of functionals should be carefully evaluated on the basis of the specific reaction and material being studied.