A Semiempirical Method to Detect and Correct DFT-Based Gas-Phase Errors and Its Application in Electrocatalysis

Abstract

Computational models of adsorption at metal surfaces are often based on DFT and make use of the generalized gradient approximation. This likely implies the presence of sizable errors in the gas-phase energetics.Here, we take a step closer toward chemical accuracy with a semiempirical method to correct the gas-phase energetics of PBE, PW91, RPBE, and BEEF-vdW exchange−correlation functionals. The proposed two-step method is tested on a data set of 27 gas-phase molecules belonging to the carbon cycle: first, the errors are pinpointed based on formation energies, and second, the respective corrections are sequentially applied to ensure the progressive lowering of the data set's mean and maximum errors. We illustrate the benefits of the method in electrocatalysis by a substantial improvement of the calculated equilibrium and onset potentials for CO 2 reduction to CO on Au, Ag, and Cu electrodes. This suggests that fast and systematic gas-phase corrections can be devised to augment the predictive power of computational catalysis models.

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

“…[11,12,26,[28][29][30][31] In fact, numerous works have reported errors when GGA functionals are used to predict gas-phase energetics. [32][33][34][35][36][37] Despite large individual errors, GGAs may as well give fair predictions of reaction enthalpies depending on the similarity of the molecules involved. In other words, GGA functionals may benefit from error cancellation when dealing with structurally similar compounds.…”

“…In other words, GGA functionals may benefit from error cancellation when dealing with structurally similar compounds. [13,38,39] For instance, systematic errors can be introduced by certain chemical structures, such as functional groups, [32][33][34] and thus GGA-based thermochemistry predictions can be closer to their experimental values when akin compounds appear on opposite sides of chemical reactions. [11,13,32] However, it is unadvisable to rely on error cancellation when studying a series of chemical reactions.…”

“…[13,38,39] For instance, systematic errors can be introduced by certain chemical structures, such as functional groups, [32][33][34] and thus GGA-based thermochemistry predictions can be closer to their experimental values when akin compounds appear on opposite sides of chemical reactions. [11,13,32] However, it is unadvisable to rely on error cancellation when studying a series of chemical reactions. Heterogenous catalysis and surface science are specific areas where it is vital to detect and correct inaccuracies in the description of free molecules because gas/liquid/solid interfaces have to be described at the same level of theory.…”

“…Guthrie [41] suggested different alternatives to calculate accurate heats of formation using DFT by following the group-additivity scheme of Benson and Buss. [42] Along those lines, Granda-Marulanda et al [32] devised a semiempirical method to correct the formation energies of gas-phase molecules belonging to the carbon cycle by pinpointing and correcting systematic errors introduced by their functional groups.…”

Computational Design of Copper doped Indium for electrocatalytic Reduction of CO2 to Formic Acid

“…With their correction scheme, on In (101) and Cu−In (101) surfaces, the equilibrium potentials of CO 2 ER can be corrected as −0.17 V (the formation of CO pathway) and −0.16 V (the formation of HCOOH pathway). In this way, the chemical accuracy is further improved, and the corrected equilibrium potentials do not affect the above conclusions on the trend for spontaneous reaction [16d] …”