Fast Correction of Errors in the DFT‐Calculated Energies of Gaseous Nitrogen‐Containing Species

Abstract

Modeling adsorption phenomena on surfaces by DFT calculations often involves substantial errors, resulting in inaccurate predictions of catalytic activities. Such errors partly stem from the inaccurate description of the energetics of free molecules. Herein, we use a semiempirical group-additivity method to correct the DFT-calculated heats of formation of 106 carbonand nitrogen-containing gaseous compounds belonging to 15 different chemical families. PBE, PW91, RPBE and BEEF-vdW initially yield mean absolute errors (MAEs) with respect to experiments in the range of 0.32-0.75 eV. After correcting the systematic errors, the overall MAEs decrease to~0.05 eV. Additionally, upon applying the corrections to three types of reaction enthalpies, the resulting MAEs are below 0.10 eV. These functional-group corrections can be used in (electro)catalysis to correct the gas-phase references necessary to evaluate equilibrium potentials and adsorption energies, predict error cancellation, and assess conflicting experimental data.

Impact of Intrinsic Density Functional Theory Errors on the Predictive Power of Nitrogen Cycle Electrocatalysis Models

“… 51 O 2 can be swiftly corrected using a semiempirical approach based on the formation energy of H 2 O. 28 , 40 , 48 In addition, ε N 2 is usually substantial and can be calculated from the ammonia synthesis reaction, as explained elsewhere 40 and in section S4 .…”

“…54 This is in line with previous works showing that compounds comprising multiple bonds, such as nitrates or carboxylic acids, display large errors. 30 , 40 …”

“…This nitrogen oxide belongs to the group of dinitrogen oxides (N 2 O x ); thus, y /2 = 1 and ε N 2 PBE = 0.34 eV. 40 Hence, we have the following: . N 2 O 5 belongs to the group of dinitrogen-containing species (N 2 O x ) and contains five oxygen atoms; thus, n O = 5.…”

“…This behavior is not random but depends on ε N 2 : if it has the same sign as the errors of the oxidized nitrogen species, ε N 2 cancels out a portion of those ( eq 5 ). 40 In addition, the small change for RPBE stems from its small ε N 2 of −0.05 eV.…”

NO Electroreduction by Transition Metal Dichalcogenides with Chalcogen Vacancies

“…The calculation details are provided in Method section in SI. For further information, please reference the recent work of Calle‐Vallejo [33b] . ΔG pH is the free energy correction of pH, which is determined by: …”